Germanosilicate compositions and methods of preparing the same

ABSTRACT

The present disclosure is directed to novel germanosilicate compositions and methods of producing the same. In particular, this disclosure describes an array of transformations originating from the extra-large-pore crystalline germanosilicate compositions, designated CIT-13, possessing 10- and 14-membered rings. Included among the new materials are the new phyllosilicate compositions, designated CIT-13P, new crystalline microporous germanosilicates including high silica versions of CIT-5 and CIT-13, with and without added metal oxides, and new germanosilicate compounds designated CIT-14 and CIT-15. The disclosure also describes methods of preparing these new germanosilicate compositions as well as the compositions themselves.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of priority to U.S. PatentApplication Ser. Nos. 62/303,604, filed Mar. 4, 2016; 62/344,025, filedJun. 1, 2016; and 62/440,742, filed Dec. 30, 2016.

TECHNICAL FIELD

The present disclosure is directed to novel germanosilicate compositionsand methods of preparing the same. In particular, this disclosuredescribes an array of transformations originating from theextra-large-pore crystalline germanosilicate compositions, designatedCIT-13, possessing 10- and 14-membered rings. Included among the newmaterials are new phyllosilicate compositions, designated CIT-13P, newcrystalline microporous high silica germanosilicates of CIT-5 and CIT-13topology, with and without added lattice metal oxides, and new highsilica germanosilicate compounds designated CIT-14 and CIT-15,possessing 8 and 12 MR and 10 MR, respectively. The disclosure alsodescribes methods of preparing these new germanosilicate compositions aswell as the compositions themselves.

BACKGROUND

Zeolites play an important role as heterogeneous catalysts and are usedin a variety of industrial settings. Initially, these materials werelargely developed to support the petroleum industry in the quest tocreate more selective, robust catalysts for making gasoline and otherfuels. Currently, these solids have emerged as specialty materials, withproperties that are based upon structure and chemical composition ableto handle specific large-scale applications. While there is aconsiderable effort that must go into bringing a new material from thediscovery phase into a commercially viable catalyst, there remains roomfor discovery of new structures with the hope that one might emerge assuperior to the existing materials.

One goal toward finding new materials has been the hope thatincreasingly large pores that retain some catalytic properties in theirinterior surfaces can be capable of handling larger feed molecules inthe oil upgrade arena.

Hence, interest remains in the discovery of new crystalline phases foruse in these applications. The present work is aimed at addressing thedeficiencies in the art in this area.

SUMMARY

This disclosure is directed to new germanosilicates derived from therecently reported crystalline microporous germanosilicates with CIT-13topology. as described in U.S. patent application Ser. No. 15/169,816,titled “Crystalline Germanosilicate Materials Of New CIT-13 Topology AndMethods Of Preparing The Same” and filed Jun. 1, 2016. This reference isincorporated by reference herein in its entirety for all purposes,including the characterization and methods of making and using materialsof the CIT-13 topology. These CIT-13 germanosilicates were preparedhydrothermally using benzyl-imidazoleum organic structuring directingagents and were characterized as possessing a three dimensionalframework having pores defined by 10- and 14-membered rings (poredimensions of 6.2×4.5 Å and 9.1×7.2 Å, respectively). These are thefirst known crystalline silicate with this architecture. Thesestructures were characterized by their powder X-ray diffraction (PXRD)patterns, their unit cell parameters, SEM micrographs, ²⁹Si MAS NMRspectroscopy, and adsorption/desorption isotherms.

The present disclosure is directed to methods of manipulating thestructures of these CIT-13 germanosilicates, having a Si/Ge ratio in arange of from 3.8 to 10, by subjecting them to several reactionconditions. The present disclosure is also directed to products derivedfrom such manipulations. In particular, the reactions include theapplication of heat, steam, and/or concentrated or dilute mineral acid,in the presence or absence of sources of various metal- ormetalloid-oxides, to provide an array of new germanosilicatecompositions. In each case, the reactions either depleted or rearrangedthe germania within the original structures, in some cases resulting ingermanosilicates of CIT-13 topologies having higher Si/Ge ratios thanaccessible through hydrothermal syntheses. These germanosilicates mayalso be (a) optionally substituted with other metal oxides; (b)germanosilicates of CIT-5 topologies also having the same or higherSi/Ge ratios than accessible through hydrothermal syntheses and alsooptionally substituted with other metal oxides; (c) phyllosilicatescomprising delaminated cfi-layers; and (d) new structures designatedCIT-14 and CIT-15, resulting from the apparent pillaring and assembly ofthe novel phyllosilicates, respectively. The relative effects of thesemanipulations depends on the germania content of the startinggermanosilicates of the present disclosure. See FIG. 1.

For example, some embodiments of the present inventions includecrystalline microporous so-called high silica-germanosilicates of CIT-13topology having Si/Ge ratios in a range of from about 25 to about 250(Forms IA and IB) These Si/Ge ratios are sigificantly higher than thoseCIT-13 structures derived from hydrothermal syntheses, such as describedin U.S. patent application Ser. No. 15/169,816 (e.g., Si/Ge=3.8 to 10).Yet, the PXRD patterns of these new high silica germansilicates showthem to be structurally analogous to those prepared by thesehydrothermal methods. The only significant difference in the PXRDpatterns is the slight shift to higher 2-θ values of the (200) and (110)crystallographic planes, consistent with a depleted germania-rich D4Runits in the high silica structures.

Other embodiments include crystalline microporous highsilica-germanosilicates of CIT-13 topology (Si/Ge in a range of about 50to about 200) which further comprise oxides of a metal or metalloid, M,where M is Al, B, Fe, Ga, Hf, Si, Sn, Ti, V, Zn, Zr, or a combinationthereof, and M is present in the CIT-13 lattices in a Si/M ratio in arange of from about 25 to about 250. (Form IB).

These high silica germanosilicates can be prepared by treating theoriginal hydrothermally-derived CIT-13 germanosilicates, having a Si/Geratio in a range of from about 4.5 to about 10, with concentratedmineral acids (e.g., ca. 1 M HNO₃) at elevated temperatures (e.g., from170-225° C.) in the presence of sources of the corresponding metal ormetalloid oxides. In some embodiments, the source of the M-oxides alsoprovide the source of the acid, for example in the case of Al(NO₃)₃. Insome specific embodiments, M is or comprises Al, B, Fe, Si, Sn, Ti,and/or Zn, most preferably Al. The high silica aluminogermanosilicatesof CIT-13 topology are characterized herein as exhibiting a ²⁷Al MAS NMRspectrum having a characteristic chemical shift at about 54 ppm,relative to 1 M aqueous aluminum nitrate solution, and as exhibiting a²⁹Si MAS NMR spectrum having characteristic chemical shifts at about−110 ppm and −115 ppm, relative to tetramethylsilane (TMS).

Still other embodiments of the present inventions include crystallinemicroporous germania-rich germansilicates of CIT-5 topology, having anSi/Ge ratio in a range of about 3.8 to about 5.4, preferably from 3.8 to5 or 3.8 to 4.35 (Form II). These compositions having CIT-5 topology maybe described as topotactic analogues (or resulting from the topotacticrearrangement) of the CIT-13 germanosilicates, in which thegermania-rich D4R units of the latter are replaced by double zig-zagchains of germania in the former.

Such structures can be prepared by heating germanosilicates, having aSi/Ge ratio in a range of about 3.8 to about 5.4, preferably from 3.8 to5 or 3.8 to 4.35, to at least one temperature in a range of from about450° C. to about 1200° C., optionally with the stepwise or simultaneousapplication of steam (at a temperature in a range of from 600° C. toabout 1000° C., more preferably in a range of from 700° C. to 900° C.),for a time sufficient so as to effect the transformation. Treating thesegermania-rich germanosilicates of CIT-5 with concentrated mineral acids(e.g., ca. 1 M HNO₃) at elevated temperatures (e.g., from 170-225° C.),results in the formation of high silica germanosilicates of CIT-5topology, having Si/Ge ratios in a range of from 30 to 200 (Forms IIIAand IIIB). When this treatment with concentrated mineral acid isaccompanied by the presence of sources of oxides of M, where M is Al, B,Fe, Ga, Hf, Si, Sn, Ti, V, Zn, Zr, or a combination thereof, theadditional M oxide are incorporated into the lattice as such that theresulting Si/M ratio is in the range of from about 25 to 250 (FormIIIB). The manner of calcining appears to affect the morphology, and insome cases the structure, of the resulting products, whether thecalcining is done in a static or rotating chamber. The use of a rotatingchamber appears to be preferred.

Certain further embodiments of the present inventions includephyllosilicates, designated CIT-13P, having Si/Ge ratios ranging fromabout 40 to about infinitiy or from about 50 to about 100 (Form IV).These may be described as structures comprising the silica-richcfi-layers resulting from the delamination of germania-richgermanosilicates of CIT-13 topology (Si/Ge=3.8 to about 4.5, 5, 5.4, oreven 5.68), in which the germania-rich D4R layers are removed, leavingsurface silanol (Si—OH) groups. Indeed, these structures can be derivedfrom reacting the germania-rich germanosilicates of either CIT-13 orCIT-5 topology with dilute mineral acid (<0.3 M) at elevatedtemperatures (e.g., 90° C. to 120° C.). These phyllosilicates CIT-13Pare characterized by a major peak in the powder X-ray diffraction (PXRD)pattern in a range of from about 6.9 to about 9 degrees 2-θ that is at ahigher angle than the corresponding major peak in the crystallinemicroporous germania-rich germanosilicate composition designated CIT-13.Again, this shift to higher 2-θ angles in the phyllosilicate isconsistent with the removal of the D4R units, and the closer packstacking of the silica-rich cfi-layers.

These phyllosilicate structures are also capable of topotacticrearrangements to form new crystalline microporous structures,designated CIT-14 (Form VI) and CIT-15 (Form V) herein. Each of theseare high silica germanosilicate frameworks, having Si/Ge ratios rangingfrom about 25 to infinity, including specific embodiments where thisratio is 75 to about 150 (in the case of CIT-14) or about 50 to about100 (in the case of CIT-15).

The CIT-14 structures (Form VI) appear to be three-dimensionalframeworks having pores defined by 8- and 12-membered rings, and havebeen characterized by PXRD patterns consistent with a structure havingsilica pillars between silica-rich cfi-layers.

The CIT-14 structures can be prepared by treating the phyllosilicates ofCIT-13P topology with a source of silica in the presence of aconcentrated mineral acid (e.g., HCl, or preferably HNO₃) at one or moretemperatures in a range of from about 165° C. to about 225° C. for atime in a range of from 12 to 48 hours to form an intermediatecomposition, then isolating and calcining the intermediate compositionso as to form a crystalline microporous silicate composition of CIT-14topology.

The CIT-15 structures (Form V) comprise a three dimensional frameworkhaving pores defined by 10-membered rings (the pores being 5.6 Å×3.8 Å),and have been characterized by PXRD patterns. The CIT-15 structures canbe prepared by calcining the phyllosilicates of CIT-13P topology at atemperature in a range of from 400° C. to about 950° C. so as to form acrystalline microporous silicate composition of CIT-15 topology.

In some aspects, the CIT-13P phyllosilicates may be characterized bytheir ability to provide the CIT-14 and CIT-15 structures, which arecrystallographically simpler to characterize, under the conditionsdescribed herein.

In certain of these embodiments, the crystalline microporous solids arepresent in their hydrogen form. In other embodiments, the crystallinemicroporous solids containing at least one metal cation salt or atransition metal or salt in their micropores.

These catalysts may be used in a variety of organic and inorganictransformations, including but not necessarily limited to:

(a) carbonylating DME with CO at low temperatures;

(b) reducing NOx with methane:

(c) cracking, hydrocracking, or dehydrogenating a hydrocarbon;

(d) dewaxing a hydrocarbon feedstock;

(d) converting paraffins to aromatics:

(e) isomerizing or disproportionating an aromatic feedstock;

(f) alkylating an aromatic hydrocarbon;

(g) oligomerizing an alkene;

(h) aminating a lower alcohol;

(i) separating and sorbing a lower alkane from a hydrocarbon feedstock;

(j) isomerizing an olefin;

(k) producing a higher molecular weight hydrocarbon from lower molecularweight hydrocarbon;

(l) reforming a hydrocarbon

(m) converting a lower alcohol or other oxygenated hydrocarbon toproduce an olefin products (including MTO);

(n) epoxiding olefins with hydrogen peroxide;

(o) reducing the content of an oxide of nitrogen contained in a gasstream in the presence of oxygen;

(p) separating nitrogen from a nitrogen-containing gas mixture; or

(q) converting synthesis gas containing hydrogen and carbon monoxide toa hydrocarbon stream; or

(r) reducing the concentration of an organic halide in an initialhydrocarbon product.

These transformations may be realized by contacting the respectivefeedstock with any one or more of the catalysts described herein, underconditions sufficient to affect the named transformation.

BRIEF DESCRIPTION OF THE DRAWINGS

The present application is further understood when read in conjunctionwith the appended drawings. For the purpose of illustrating the subjectmatter, there are shown in the drawings exemplary embodiments of thesubject matter; however, the presently disclosed subject matter is notlimited to the specific methods, devices, and systems disclosed. Inaddition, the drawings are not necessarily drawn to scale. In thedrawings:

FIG. 1 shows illustrative schemes of some of the transformationsdiscussed in this disclosure.

FIG. 2 shows the relationship of the Si/Ge ratio with respect to gelsand calcined products for CIT-13 syntheses as characterized by EDS (fromU.S. patent application Ser. No. 15/169,816).

FIG. 3 shows the deconvoluted ²⁹Si 8K MAS solid-state NMR spectra ofas-calcined CIT-13 (Si/Ge=5.0), with chemical shifts at −104.6 ppm(3.8%), −107.31 ppm (4.5%), −110.47 ppm (17.9%), −113.05 ppm (32.0%),−116.06 ppm (16.5%), −118.03 ppm (25.1%). Solid line is actual spectrum;dotted line is sum of the indicated peaks (from U.S. patent applicationSer. No. 15/169,816).

FIG. 4 shows representative PXRD data for hydrothermally synthesizedCIT-13, theoretical and experimentally derived. See Table 10 fortheoretical peak listings.

FIG. 5 shows exemplary PXRD data for silica-rich CIT-13 germanosilicate.See Table 2 for specific details.

FIG. 6 shows illustrative morphologies for products resulting from thereaction of 1 M nitric acid with hydrothermally synthesized CIT-13. SeeTable 2 for specific details.

FIGS. 7(A-B) show portions of the PXRD patterns for products of thereaction of 1 M nitric acid with hydrothermally synthesized CIT-13,reflecting the shift to higher angles of 2-θ after nitric acidtreatments, showing shrinkage of (200) and (110) crystallographic planeswith increasing Si.Ge ratios. FIG. 7(A) shows full pattern; FIG. 7(B)shows selected peaks

FIG. 8 illustrate the relative positions of the (200) and (110)crystallographic planes in the CIT-13 topology.

FIG. 9 shows representative data for the results ofalumination/degermanation of CIT-13 using Al(NO₃)₃. See Table 3 forspecific details.

FIG. 10 show ²⁷Al MAS NMR data for the aluminated CIT-13germanosilicates, obtained before and after washing the first formedproduct of the alumination to remove the octahedral alumina. The upperspectrum showed that about ⅔ of the alumina was extra-framework.Exchanging with Na⁺ and washing removed much of this extra-frameworkoctahedral alumina.

FIGS. 11(A-B) show deconvoluted ²⁹Si 8K MAS solid-state NMR spectra ofCIT-13 aluminosilicates at different alumina loading levels.

FIG. 12 shows the removal of the infrared peak at about 1000 cm⁻¹ thathas been associated with a Ge—O—Si asymmetric vibration in the FTIRspectrum with following degermanation of CIT-13 germanosilicate(Si/Ge=5) with nitric acid.

FIG. 13 shows a schematic representation of the changes associated withthe transformation of CIT-13 germanosilicates to CIT-5 germanosilicateswith the application of heat and optional steam.

FIG. 14 shows a schematic representation of the pore size channeldimensions associated with CIT-5 germanosilicates. Pore data was adaptedfrom IZA-Structure Database.

FIG. 15 shows PXRD pattern changes associated with calcining/steaming ofCIT-13 germanosilicate (Si/Ge=3.78)

FIG. 16 shows PXRD pattern changes associated with calcining/steaming ofB/Ge CIT-13 germanosilicate (Si/Ge=3.92, B<1 atom %).

FIG. 17 shows absence of PXRD pattern changes associated withcalcining/steaming of CIT-13 germanosilicate (Si/Ge=6.38).

FIG. 18 shows PXRD pattern changes observed during calcining/steaming ofCIT-13 germanosilicate, showing presence of either incomplete conversionto CIT-15 or reaction intermediate.

FIG. 19(A-F) shows product morphologies after calcining/steaming ofCIT-13 germanosilicate. See Table 5. Results shown for FIG. 19(A):static oven, Si/Ge=3.84 (no transformation); FIG. 19(B): rotating oven,Si/Ge=4.10 (CIT-5); FIG. 19(C): rotating oven, Si/Ge=3.87 (CIT-5); FIG.19(D): static oven, Si/Ge=3.78 (no transformation); FIG. 19(E): rotatingoven, Si/Ge=6.60 (no transformation); FIG. 19(F): static oven,Si/Ge=6.38 (no transformation).

FIGS. 20(A-B) shows PXRD patterns for CIT-13 aluminosilicates withvarying alumina content. See Tables 6 and 7 for description of Examples1, 2, and 3.

FIG. 21 shows the ²⁷Al MAS NMR spectrum for the CIT-5 aluminosilicatedescribed in Example 1 of Table 6.

FIG. 22 shows PXRD pattern changes observed associated with treatingCIT-13 germanosilicate having various Si/Ge ratios, showingdelamination/degermanation to form CIT-13P.

FIG. 23 shows a schematic representation of the idealized structure ofCIT-13P.

FIG. 24 shows the PXRD patterns of the precursor CIT-13 germanosilicatesused to prepare the CIT-13P phyllosilicates over a range of Si/Geratios, and FIG. 25 shows the PXRD patterns of the corresponding CIT-13Pphyllosilicates prepared from these precursors. The calcined precursorswere treated with 0.1 M hydrochloric acid for 24 hours at 99° C. Y-axisnumbers are Si/Ge ratios for the precursor CIT-13 germanosilicates.

FIGS. 26(A-B) show a comparison of ²⁹Si and ¹H-²⁹Si CP MAS NMR,respectively, for CIP-13P.

FIG. 27 shows a theoretical PXRD data for CIT-15. See Table 10 fortheoretical peak listings.

FIG. 28 shows a schematic representation of the pore size channeldimensions of CIT-15 germanosilicate.

FIG. 29 shows a comparison of experimentally derived and theoretic PXRDpatterns for CIT-15 germanosilicate.

FIG. 30 shows a schematic representation of the changes thought to beassociated with the transformation of CIT-13P phyllosilicates to CIT-15germanosilicates. The dotted circles is thought to represent theplacement position (into the page) of the C₁₋₁₂ alkyl amines during thepreconditioning.

FIG. 31 shows the PXRD patterns associated with the organization ofCIT-13P at varying Si/Ge precursor ratios into CIT-14 germanisilicatedunder pillaring conditions, showing the substantial constancy of themain peaks in the PXRD pattern of CIT-14 germanosilicates over the rangeof ratios.

FIG. 32 shows the PXRD patterns associated with CIT-14 germanosilicatesincluding the effect of precursor Si/Ge ratios on the position of themain peaks. See Table 9.

FIGS. 33(A-B) illustrate the structure believed to represent CIT-14 andits theoretical PXRD data (FIG. 33(A)) and pore channel dimensions (FIG.33(B)). See Table 10 for theoretical peak listings.

FIG. 34 shows a schematic representation of the changes thought to beassociated with the transformation of CIT-13P phyllosilicates to CIT-14germanosilicates. “SiO₂” represents a source of silica.

FIG. 35 shows a representative 29 Si MAS NMR of a CIT-14germanosilicate, containing a plurality of Q⁴ environments.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

The present invention is directed to new compositions of matter,including those comprising crystalline microporous silicates, includinggermanosilicates, and methods of making and using these compositions

The present invention may be understood more readily by reference to thefollowing description taken in connection with the accompanying Figuresand Examples, all of which form a part of this disclosure. It is to beunderstood that this invention is not limited to the specific products,methods, conditions or parameters described or shown herein, and thatthe terminology used herein is for the purpose of describing particularembodiments by way of example only and is not intended to be limiting ofany claimed invention. Similarly, unless specifically otherwise stated,any description as to a possible mechanism or mode of action or reasonfor improvement is meant to be illustrative only, and the inventionherein is not to be constrained by the correctness or incorrectness ofany such suggested mechanism or mode of action or reason forimprovement. Throughout this text, it is recognized that thedescriptions refer to compositions and methods of making and using saidcompositions. That is, where the disclosure describes or claims afeature or embodiment associated with a composition or a method ofmaking or using a composition, it is appreciated that such a descriptionor claim is intended to extend these features or embodiment toembodiments in each of these contexts (i.e., compositions, methods ofmaking, and methods of using). Where methods of treatment are described,unless otherwise specifically excluded, additional embodiments providethat the product compositions are isolated and optionally post-treatedin a manner consistent with molecular sieve or zeolite syntheses.

Hydrothermally Prepared Germanosilicate Compositions of CIT-13 Topology.

This disclosure is directed to new germanosilicates derived from therecently reported crystalline germanosilicate phase molecular sieve withCIT-13 topology. This CIT-13 topology is described in U.S. patentapplication Ser. No. 15/169,816, filed Jun. 1, 2016, which isincorporated by reference herein in its entirety for all purposes,including the characterization and methods of making and using materialsof the CIT-13 topology. These reported crystalline microporousgermanosilicate CIT-13 structures were prepared hydrothermally usingbenzyl-imidazolium organic structuring directing agents andcharacterized as possessing a three dimensional framework having poresdefined by 10- and 14-membered rings (pore dimensions of 6.2×4.5 Å and9.1×7.2 Å, respectively), are the first known crystalline silicate withthis architecture. These structures, prepared over a Si/Ge range of 3.8to 10 (see FIG. 2) were variously characterized by their powder X-raydiffraction (PXRD) patterns, their unit cell parameters (Table 1), SEMmicrographs, ²⁹Si MAS NMR spectroscopy, and porosimetry data. The ²⁹SiMAS NMR spectra showed a plurality of silicon environments (FIG. 3),when Si/Ge=5.0, the complexity deriving from the presence of thegermania-rich D4R units positioned between the silica-rich layers (seeinset, FIG. 4).

TABLE 1 Unit cell parameters for hydrotermally derived CIT-13germanosilicates, as provided in U.S. patent application Ser. No.,15/169,816 Space group Cmmm a (Å) 27.4374(5) b (Å) 13.8000(2) c (Å)10.2910(2) V (Å³) 3896.6(1) Z 8 ρ (g/cm³) 2.144(2) λ (Å) 0.776381(1)

For purposes of the present discussion, these structures are describedin terms of silica-rich cfi-layers, comprising tetrahedral arrays ofsilica groups, that are joined by germania-rich D4R units (see insetFIG. 4). The silica-rich cfi-layers, are so-called because they arecomprised of cfi-composite building units, its name coming from theframework type CFI, of which CIT-5 is a notable example. The term“silica-rich’ is used to allow for the presence of other metal ormetalloid oxides present in this ideal silica lattice.

As is shown elsewhere herein, the transformations described hereingenerally retain the structure of these silica-rich cfi-layers, asevidenced crystallographically, and the product structures differ in theways in which these silica-rich cfi-layers are joined with one another.The term “joined” refers to the bonding of of an arrangement of germaniaor other oxides (e.g., with D4R, double zig zag, pillared, or otherarrangements between the layers, in positions which hold the silica-richcfi-layers separate and parallel or practically parallel to one another.In the absence of such oxide bonding, and in some embodiments, thesilica-rich cfi-layers comprise silanol (Si—OH) groups in at least someof the positions otherwise occupied by the bonded germania or otheroxides.

The present application discloses new silicate compositions derived fromthe transformation of these crystalline microporous germanosilicatecompositions designated CIT-13, having Si/Ge ratios in a range of fromabout 3.8 to about 10. Just as these germanosilicate precursors may alsocontain other metal or metalloid oxides in the lattice, so also can theresulting products contain the same or similar metal or metalloid oxidesin their lattice before or after the transformations described herein.

For the sake of discussion herein, when used in the context of anoverall composition, the term “germania-rich” refers to agermanosilicate composition having sufficient germania to favor adelamination as described below. Generally, such delaminations occurwith germanosilicates of CIT-5 and CIT-13 topologies where the Si/Ge isless than about 5.68, 54, 5, 4.4, or 4.35. Having said this, dependingon the accuracy of the Si and Ge analyses, some compositions have beenseen to delaminate at higher apparent ratios, for example, at Si/Geratios as high as 5.4 or 5.68 (see, e.g., FIGS. 24, 25, and 31). Whenused in the context of the D4R or double zig-zag building block (e.g.,“germania-rich D4R units), the germania content is much higher, and theSi/Ge ratios can approach or be practically zero (i.e., these units arepractically entirely germania). By contrast, when used in the context ofan overall composition, the term “silica-rich” refers to a compositionwhich is not prone to delamination, presumably because of the silicacontent in the joining units is too refractory. Generally, this term isused in the context when the Si/Ge ratio is in a range of from about 5.4to about 10. The term “high silica” refers to Si/Ge ratios in excess ofthis upper boundary; i.e., greater than about 10. The compositions ofthe present disclosure to which this term is applied generally has Si/Geratios in a range of from about 25 to about 250, or higher.

I. Reactions of Silica-Rich Germanosilicates of CIT-13 Topology withConcentrated Mineral Acids to Form High Silica GermanosilicateCompositions of CIT-13 Topology (Crystal Forms IA and IB)

Form IA:

Among the transformations being disclosed herein are the products whichcan be derived from the treatment of the silica-rich CIT-13germanosilicates with concentrated mineral acids. The first of these newclasses of materials includes embodiments which are crystallinemicroporous high silica-CIT-13 germanosilicates of having Si/Ge ratiosin a range of from about 25 to about 250. These Si/Ge ratios of thesematerials are sigificantly higher than those CIT-13 germanosilicatessynthesized from hydrothermal crystallizations, yet, the PXRD patternsof these high silica CIT-13 germansilicates show them to be structurallyanalogous to those prepared by these hydrothermal methods. The onlysignificant difference in the PXRD patterns is the slight shift tohigher 2-θ values of the (200) and (110) crystallographic planes,consistent with the relative amounts of germania-rich D4R units in therespective structures.

Form IB:

Other embodiments include crystalline microporous highsilica-germanosilicates of CIT-13 topology (again, with Si/Ge ratios ina range of about 25 to about 250) which further comprise oxides of M,where M is Al, B, Fe, Ga, Hf, Si, Sn, Ti, V, Zn, Zr, or a combinationthereof, and M is present in the CIT-13 lattices in a Si/M ratio in arange of from about 15 to about 200, preferably from about about 25 toabout 250.

These high silica CIT-13 germanosilicates can be prepared by treatingthe original hydrothermally-derived CIT-13 germanosilicates having aSi/Ge ratio in a range of from about 4.5 to about 10, with concentratedmineral acids at elevated temperatures. In particular embodiments,“concentrated mineral acids” are defined broadly elsewhere herein, butin preferred embodiments, the mineral is or comprises nitric acid atconcentrations in a range of 0.9 to 1.1 M. Similarly, the term “elevatedtemperature” is also defined elsewhere, but in this context is in arange of from about 160° C. to about 230° C., preferably about 175° C.to about 195° C.

As this transformation appears to be mainly a degermanation reaction,where the original hydrothermally-derived CIT-13 germanosilicatescontain other metal or metalloid oxides in the framework, for example,in the cfi-layers, the resulting high silica CIT-13 germanosilicatesalso contain these features.

In expanded embodiments, these high silica CIT-13 germanosilicates haveSi/Ge ratios in a range of from about 15 to about 250, and may bedescribed in terms of Si/Ge ratios in one or more ranges from about 15to about 25, from about 25 to about 50, from about 50 to about 75, fromabout 75 to about 100, from about 100 to about 125, from about 125 toabout 150, from about 150 to about 200, and from about 200 to about 250or higher (e.g., with the complete elimination of the germania).

In one exemplary set of representative experiments, silica-rich CIT-13germanosilicate (Si/Ge=5.03±0.48) was treated with nitric acid (1 M) at190° C. for 1-3 days (see Table 2, FIG. 5).

TABLE 2 Results of extracting samples of silica-rich CIT-13germanosilicates in aqueous nitric acid (1M) at 190° C. for varioustimes; see FIG. 5 for corresponding PXRD patterns Sample Time ofExposure (days) Framework EDS (Si/Ge) 1 0 (starting material) CIT-135.03 ± 0.48 2 1 day CIT-13 26.5 ± 16.1 3 2 x one day CIT-13 67.2 ± 27.14 3 x one day CIT-13 55.6 ± 10.5 5 3 days CIT-13 122 ± 26 In each case, the CIT-13 framework was retained, while the Si/Ge ratioincreased by factors of 5 to 25, with associated changes in morphologiesof the resulting products (FIG. 6). Lesser or more severe treatments (byboth time of exposure and temperature) may allow for ratios of fromabout 15 to about 250, or higher

The high silica CIT-13 germanosilicates exhibit PXRD patterns consistentwith their CIT-13 topologies, including the expected shift of thediffraction peaks associated with the (200) and (110) crystallographicplanes to higher angles, relative to their lower silica analogs. Again,the higher 2-theta diffraction peaks associated with thesecrystallographic planes in the high silica CIT-13 germanosilicatesreflect a more proximate spacing of these crystallographic planes in theproduct high silica CIT-13 materials than those of the latterhydrothermally treated starting materials. See FIGS. 7(A-B) and 8. Forexample, a high silica composition having Si/Ge of about 122 shows 2-θof 6.7 and 7.38 for the (200) and (110) plane, corresponding to a shiftof about 0.2 deg 2-theta relative to the corresponding silica-richmaterial (Si/Ge=5)

When the high silica CIT-13 germanosilicates are treated withconcentrated mineral acids in the presence of source of metal ormetalloid oxides, M-oxides, these oxides can become incorporated intothe CIT-13 lattice, displacing at least a portion of the germania-richD4R units of the CIT-13 compositions. See Table 3 and FIG. 9.

TABLE 3 Alumination of CIT-13 Germanosilicate with 1M aqueous Al(NO₃)₃at 170° C. Time Example (days) PXRD Result Si/Al (EDS) Si/Ge (EDS) 1 0Original CIT-13 infinity  5.08 ± 0.48 2 1 Preserved CIT-13 11.7 ± 0.4104 ± 14 3 3 Preserved CIT-13 10.9 ± 0.3 113 ± 13

This reactivity has yielded new compositions which are both high insilica content and having incorporated metal or metalloid oxides in thegermanosilica CIT-13 structures. These new structures are alsoconsidered separate embodiments of the present invention. In someembodiments, the source of the M-oxides also provides the source of theacid, for example in the case of Al(NO₃)₃. In some specific embodiments,M is or comprises Al, B, Fe, Ga, Hf, Si, Sn, Ti, V, Zn, Zr, or acombination thereof, preferably Al, B, Fe, Si, Sn, Ti, and/or Zn, mostpreferably Al. The high silica aluminogermanosilicates of CIT-13topology are characterized herein as exhibiting PXRD patterns asdescribed above (again, showing a displacement of the diffraction peaksassociated with the (200) and (110) crystallographic planes. In thesecases, the high silica CIT-13 germanosilicates further compriseM-oxides, where the Si/M ratio is in a range of from about 15 to about200, preferably from about 30 to 200, and more preferably from about 40to about 170.

In specific embodiments, the high silica CIT-13 germanosilicate is alsoan aluminosilicate (i.e., an aluminogermanosilicate), where aluminum isincorporated into the lattice, either or both in the D4R units or in thecfi-layers. The ²⁷Al MAS NMR spectra of the CIT-13 aluminosilicates showcharacteristic chemical shifts at about 54 ppm, relative to 1 M aqueousaluminum nitrate solution, consistent with a tetrahedral environment ofthe aluminum. In some embodiments, the aluminosilicate further exhibitsadditional chemical shifts at or about 64.7 ppm and/or at or about 47.0ppm. See FIG. 10. In other embodiments, some of the the aluminum isadditionally present ex-framework, in the pore structures, as octahedralalumina. Some or all of this extra-framework alumina can be removed bychemical washing with an appropriate acid known to be useful for thispurpose.

The CIT-13 aluminosilicates also exhibit ²⁹Si MAS NMR spectra havingcharacteristic chemical shifts at about −110 ppm and −115 ppm, relativeto tetramethylsilane (TMS). See FIG. 11(A). In some cases, it ispossible to detect additional shifts at about −108 ppm, attributed to Siin the D4R position, when the silica is sufficiently present in thisenvironment. See FIG. 11(B), bottom spectrum.

Infrared spectroscopy can also provide some insights as to the frameworkelemental compositions accompanying these degermanation reactions. Insome related systems, an infrared peak at about 1000 cm⁻¹ has beenassociated with a Ge—O—Si asymmetric vibration. As shown in FIG. 12,this peak appears in the CIT-13 germanosilicate (Si/Ge=5) and is removedor shifted on treatment with the HNO₃.

II. Reactions of Germania-Rich Germanosilicates of CIT-13 Topology . . .

The lability of the germania-rich D4R structures in the CIT-13germanosilicates offers a rich chemistry, which differs depending on thegermania content of the CIT-13 compositions. Considering first only thegermania-rich germanosilicates, this can provide for delamination toform phyllosilicates (designated CIT-13P herein) or for topotacticrearrangements to form germania-rich germanosilicates of CIT-5 topology,which can further yield other new compositions. These are discussedseparately herein.

A. The Application of Heat/Steam in the Absence of Added Mineral Acidsto Form Germania-Rich Germanosilicates of CIT-5 Topology (Crystal FormII)

The germania-rich CIT-13 germanosilicates, where the Si/Ge ratio is in arange of from about 3.8 to about 5.4, preferably in a range of fromabout 3.8 to about 5, 4.5 or 4.35, topotactically rearrange in thepresence of heat (air-calcining), and optionally/additionally in thepresence of steam, to transform the CIT-13 topology to the first knowngermanosilicate compositions of CIT-5 topology. As shown schematicallyin FIG. 13, the transformation is consistent with the net rearrangementof at least a portion, and preferably all of, the germania-rich D4Runits in the CIT-13 structure to a double zig-zag chain arrangement ofthe germania in the CIT-5 structure. Accordingly, the transformation ofthe CIT-13 topology to the CIT-5 topology typically and practicallypreserves the Si/Ge ratio of the former in the latter, while leaving thesilica-rich cfi-layers largely unaffected. Also as illustrated in FIG.13, the germania rich CIT-5 germanosilicates retains/contains the14-membered pore, and differs from the absence of the 10-membered poresof the CIT-13 precursor.

Certain embodiments, then, provide for germanosilicates of the CIT-5topology, having Si/Ge ratios in the range of from about 3.8 to about5.4, or may be characterized as having a combination of two or more ofthe ratio ranges of from about 3.8 to about 3.9, from about 3.9 to about4.0, from about 4.0 to about 4.1, from about 4.1 to about 4.2, fromabout 4.2 to about 4.25, from about 4.25 to about 4.3, from about 4.3 toabout 4.35, from about 4.35 to about 4.3, from about 4.3 to about 4.35,from about 4.35 to about 4.5, from about 4.5 to about 4.55, from about4.55 to about 4.6, from about 4.5 to about 4.65, from about 4.65 toabout 4.7. from about 4.6 to about 4.75, from about 4.75 to about 4.8,from about 4.7 to about 4.85, from about 4.85 to about 4.9, from about4.9 to about 4.95, from about 4.95 to about 5.0, from about 5.0 to about5.05, from about 5.05 to about 5.1, from about 5.1 to about 5.15. fromabout 5.15 to about 5.2, from about 5.2 to about 5.25, from about 5.25to about 5.3, from about 5.3 to about 5.35, or from about 5.35 to about5.4.

It should be appreciated that, since transformation of the CIT-13 to theCIT-5 topologies appears to effect mainly the D4R units of the CIT-13germanosilicates, the metal or metalloid oxide content within thecfi-layers of the CIT-5 products should mirror and be available from theCIT-13 precursors. For example, the lattice framework of thegermania-rich CIT-5 may contain oxides of aluminum, boron, gallium,hafnium, iron, tin, titanium, vanadium, zinc, zirconium, or combinationor mixture thereof derived from the precursor CIT-13 material.

A comparison of the PXRD data for these germania rich CIT-5germanosilicates with their pure silicate analogs shows a goodcorrelation, consistent with the CIT-5 structure. See Table 4 and FIGS.15-18. In certain embodiments, then, the PXRDs of the germania richCIT-5 germanosilicates are at least qualitative similar to othercompositions of CIT-5 topologies, and in some cases may contain at least5 of the characteristic peaks provided in Table 4 for this crystallineform. As is typically the case in metal substituted analogs, thepresence of addition metal or metalloid oxides in the lattice may alsobe characterized by the PXRD patterns in Table 4. Some variability inthe exact position is to be expected, based on the substitution of othermetal oxides, and the skill artisan would be capable of recognizingthese variations.

TABLE 4 Comparison of PXRD Data for Pure Silica CIT-5 and Ge- richGermanosilicate CIT-5; all data in deg. 2θ Pure silica CIT-5* Ge-CIT-5**Miller Indices** 6.95 ± 0.15 (vs) 7.02 ± 0.15 002  7.3 ± 0.15 (s-vs)7.38 ± 0.15 101 — 13.04 ± 0.15  200 13.9 ± 0.15 (w-s) ~13.9 004 19.0 ±0.15 (w-vs) ~19.0 204 20.0 ± 0.15 (m-vs) ~20.0 112 20.5 ± 0.15 (w-s) — —20.9 ± 0.15 (w-vs) — — 24.6 ± 0.15 (w-m) — — 26.8 ± 0.15 (w-vs) 27.06 ±0.15  412 *Data from U.S. Pat. No. 6,043,179 (reported relativeintensities provided in parentheses). **GE-rich germanosilicate CIT-5

Also as described elsewhere herein, these germania-rich CIT-5germanosilicates may be prepared by calcining and/or steam treatingtheir germania-rich CIT-13 topologs, having Si/Ge ratios in a range ofabout 3.8 to about 5, 4.5, or 4.35, and in certain embodiments, thethese germania-rich CIT-5 germanosilicates may be characterized as theproduct of these treatments. In some embodiments, the germania-richCIT-13 germanosilicates are calcined in air or an otherwise oxidizingenvironment. In this case, calcining may include treating at one or moretemperatures in a range of from about 500° C. to about 1200° C., whichmay be characterized as one or more ranges of from 500° C. to about 600°C., from 600° C. to 700° C., from 700° C. to 800° C., from 800° C. to900° C., from 900° C. to 1000° C., from 1000° C. to 1100° C., or fromabout 1100° C. to about 1200° C., more preferably in a range of fromabout 700° C. to about 900° C., for a time sufficient so as to effectthe conversion. Such time can typically range from 6 to 72 hours, thoughlesser times are generally preferred simply for economic reasons. Again,these treatments are done in the absence of acid materials, as thepresent of such acid is described herein as yielding other products.

The topotactic transformation may also be accomplish by the use ofsteam, and some embodiments provide for the use of steam by itself andother embodiments call for the use of steam after calcining. In thoseembodiments where the calcining is followed by the application of steam,the steam is provided at autologous pressures at one or moretemperatures in a range of from from 600° C. to about 1000° C.,preferably in a range of from 700° C. to 900° C.

The manner in which the CIT-13 precursor materials are synthesizedaffects the eventual transformation to form the CIT-5 topology. In somecases, use of the different types of reactors can lead to differentmorphologies, and even different products. In separate embodiments, thesynthesis of the CIT-13 precursor done in a static oven. In otherembodiments, the synthesis of the CIT-13 precursor is done in a movingchamber, preferably a rotating chamber. Rotating chambers appear toyield finer crystals. See, e.g., Table 5 and FIGS. 15-17. As shown inTable 5, Ge-rich CIT-13 treated in rotary ovens transformed togermanosilicate CIT-5 at 580° C. (Si/Ge=3.87) (FIG. 15). Even after aharsh steaming process at 800° C./8 hr/T_(bubbler)=80° C., the CIT-5framework of the originally prepared material was not broken (FIG. 17).After a calcination at 580° C. for 6 hr, CIT-13 (Si/Ge=4.22) hadtransformed to somewhere between CIT-13 and CIT-5, the PXPD profileshowing both CIT-13 peaks and CIT-5 peaks (FIG. 18). This stage maysimply be a mixture of CIT-13 phase and CIT-5 phase. Alternatively, thisstage can be a dictionary-definition intermediate phase that is notCIT-13 nor CIT-5. This material completely transformed into CIT-5 aftera 800° C./8 hr calcination A Ge-poor CIT-13 (Si/Ge=6.38) showed no phasetransformation at any temperature. Even after a harsh steaming processat 800° C./8 hr/T_(bubbler)=80° C., the CIT-13 framework remained. Otherexperiments confirmed these limits. See FIGS. 19(A-F).

TABLE 5 Results of the transformations of CIT-13 germanosilicates toCIT-5 germanosilicates using steam/calcination. EDS Si/Ge CIT-13 toCIT-5 Transformation Ratio of Precursor Calcination Calcination SteamingCIT-13 Synthesis 580° C. for 6 800° C. for 8 800° C. Precursor OvenCondition hours hours for 8 hours 3.84 Static No No 3.87 Rotary Yes YesYes 4.06 Rotary Yes Yes — 4.1 Rotary Yes Yes — 4.22 Rotary Yes — — 4.28Static Yes — — 4.31 Rotary Yes — — 4.35 Rotary Mix* Yes 4.72 Static NoNo — 6.38 Rotary No No No See text, and FIGS. 15 to 19.

A1. Subsequent Reactions of the Germania-Rich Germanosilicates of CIT-5Topology with Mineral Acid to Form High Silica Germanosilicates of CIT-5Topology (Crystal Forms IIIA and IIIB)

Form IIIA.

The treatment of these germania-rich germanosilicates of CIT-5 topology(Form (II)) with concentrated mineral acids, such as HNO₃, at elevatedtemperatures (e.g., from 170-225° C.), results in the degermanation ofthe lattice, with the with retention of the CIT-5 framework, asevidenced by the characteristic PXRD patterns. As with many of thesetransformations, the heating/steaming can be done repeatedly to increasethe Si/Ge ratios. This represents the first high silica germanosilicatehaving CIT-5 topology. These high-silica germanosilicates of CIT-5topology exhibited Si/Ge ratios ranging from 25-250, as determined byEDS. In other embodiments, these high-silica germanosilicates may bedescribed as exhibiting Si/Ge ratios in one or more ranges of from 15 to25, from 25 to 30, from 30 to 40, from 40 to 50, from 50 to 60, from 60to 70, from 70 to 80, from 80 to 90, from 100 to 110, from 110 to 120,from 120 to 130, from 130 to 140, from 140 to 150, from 150 to 200, andfrom 200 to 250, or higher.

Form IIIB.

When these germania-rich germanosilicates of CIT-5 topology are treatedwith concentrated mineral acids in the additional presence of source ofother metal or metalloid oxides, these oxides can be incorporated intothe CIT-5 lattice. In some embodiments, these metal or metalloid oxides,M, can be Al, B, Fe, Ga, Hf, Si, Sn, Ti, V, Zn, Zr, or a combinationthereof. In preferred embodiments, M is Al. In some embodiments, theresulting Si/M ratio is in the range of from about 25 to 250, and thematerial can be characterized as exhibiting Si/M ratios in one or moreranges of from 15 to 25, from 25 to 30, from 30 to 40, from 40 to 50,from 50 to 60, from 60 to 70, from 70 to 80, from 80 to 90, from 100 to110, from 110 to 120, from 120 to 130, from 130 to 140, from 140 to 150,from 150 to 200, and from 200 to 250, or higher. In specificembodiments, M is Al; i.e., the product is an aluminogermanosilicate ofCIT-5 topology.

In one representative series of experiments (Tables 6 and 7),germania-rich germanosilicate CIT-5 (Z-2, produced by the transformationof germania-rich germanosilicate CIT-13 (Z-1) was treated with 1 Mnitric acid and the presence or absence of 1 M aluminum nitrate at 185°C. for 24 hours. The degermanation and alumination was donesimultaneously without any collapse of CIT-5 frameworks. Interestingly,in some circumstances, when treated only with 1 M aluminum nitrate (w/onitric acid), Ge-CIT-5 was collapsed. Without being bound by thecorrectness of any particular theory, this may result from the fact thatthe pH of the 1 M aluminum nitrate (2.1-2.4) was higher than theisoelectic point (known as approx. 2) of the germanosilicate, and thatkeeping the pH of the acid is an important consideration in preparingthese materials.

TABLE 6 Treatment of Germania-Rich CIT-5 to Form High Silica CIT-5 andHigh Silica Aluminosilicate CIT-5; 24 hours at 185° C. (see also Table 7and FIG. 20). Nominal Nominal Nominal Nominal Result EDS AnalysesExample [Al³⁺] [H⁺] [NO₃ ⁻] pH (XRD) Si (%) Ge (%) Al % (%) “Broken”*  1 M — 3 M 2.45 Broken 91% 1.6 ± 0.1% 7.0 ± 0.4 CIT-5 1 0.5 M 0.5 M 2 M0.3 CIT-5 95% 2.0 ± 0.2% 2.5 ± 0.3 2 0.1 M 0.9 M 1.2 M   0.05 CIT-5 97%2.6 ± 0.4% ~0.7% 3 —   1 M 1 M 0.00 CIT-5 97% 3.0 ± 0.4% — *CIT-5Framework not preserved

TABLE 7 Comparison of PXRD Data for pure silica CIT-5 and high silicaCIT-5 germanosilicates Miller Example 1 Example 2 Example 3 Pure silicaCIT-5* Ge-CIT-5** Indices** (°) (°) (°) 6.95 ± 0.15 (vs) 7.02 ± 0.15 0027.08 ± 0.15 7.00 ± 0.15 7.08 ± 0.15  7.3 ± 0.15 (s-vs) 7.38 ± 0.15 1017.34 ± 0.15 7.38 ± 0.15 7.48 ± 0.15 — 13.04 ± 0.15  200 ~13.0 ~13.1~13.1 13.9 ± 0.15 (w-s) ~13.9 004 ~13.9 ~14.0 ~14.0 19.0 ± 0.15 (w-vs)~19.0 204 ~19.2 ~19.2 ~19.2 20.0 ± 0.15 (m-vs) ~20.0 112 ~20.0 ~20.1~20.1 20.5 ± 0.15 (w-s) — — — — — 20.9 ± 0.15 (w-vs) — — — — — 24.6 ±0.15 (w-m) — — — — — 26.8 ± 0.15 (w-vs) 27.06 ± 0.15  412 ~27.1 ~27.1~27.2 *Data from U.S. Pat. No. 6,043,179; parenthetical relativeintensities) **Ge-rich germanosilicate CIT-5; all data in deg. 2θIn each case, the product had a PXRD pattern that was consistent that ofother aluminosilicates having CIT-5 topology (FIG. 20). As shown inTable 6, the Si/Al ratios were 37-170, and Si/Ge ratios were 33-47depending on the composition of mixture solutions. Finally, ²⁷Al MAS NMRshowed that aluminum atoms had been incorporated in frameworks (FIG.21).

B. With Dilute Mineral Acid to Form Phyllosilicates (CIT-13P)(CrystalForm IV)

Further embodiments of the present inventions include phyllosilicates,designated CIT-13P (Form IV), having Si/Ge ratios ranging from about 40to infinity. These may be described as structures comprising thesilica-rich cfi-layers, which can optionally be derived from thedelamination of germania-rich CIT-5 (precursor having a Si/Ge ratio of3.8 to about 5.4) or CIT-13 germanosilicates (having Si/Ge ratios in arange of from 3.8 to about 5.68, 5.4, 5, or 4.5). See FIG. 22.

The germania-rich D4R or double zig zag layers of the precursors areremoved, with the corresponding introduction of surface silanol (Si—OH)groups. Indeed, these structures can be derived from reacting thegermania-rich germanosilicates of CIT-13 or CIT-5 (Form II) topologywith dilute mineral acid (<0.3 M) at intermediate elevated temperatures(e.g., 90° C. to 120° C.). These phyllosilicates CIT-13P may also beindependently described as (germano-) silicate compositions consistingessentially of siloxylated silica-rich cfi-layers (of the CIT-13framework) While FIG. 23 shows an idealized pure silica structure, insome embodiments, the CIT-13P contains residual germania units attached.(an Si/Ge ratio of 50 to 100 indicates the presence of 1-2% Ge).

In separate independent embodiments, the phyllosilicate CIT-13Pmaterials contain or are free of defects, which may result from thehydrolysis of the silica-rich cfi-layers (level of defects, for example,less than 3, 2, 1, or 0.5%, as determined by ¹H-²⁹Si CPMAS NMR and ²⁹SiCPMAS-NMR).

In some embodiments, the CIT-13P phyllosilicates have a Si/Ge ratio in arange of from about 40 to infinity. The compositions may also bedescribed in terms of intermediate ratio ranges, for example one or moreof the ranges of ratios from about 40 to 50, from 50 to 60, from 60 to80, from 80 to 100, from 100 to 200, and from 200 to infinity.

These phyllosilicates are characterized by a major peak in the powderX-ray diffraction (PXRD) pattern in a range of from about 6.9 to about 9degrees 2-θ. See FIGS. 24-25. In other embodiments, the major peak inthe PXRD pattern is a peak in a range of from about 7.0±0.2 degrees 2-θto about 8.1±0.2 degrees 2-θ. This major peak is at a higher angle thanthe corresponding major peak in the crystalline microporousgermania-rich CIT-13 germanosilicate composition from which they may bederived, and is consistent with the removal of the D4R units and thecloser pack stacking of the stacked silica-rich cfi-layers. Somevariance is seen in the absolute position of this major peak. This canbe explained when one appreciates that the peak is attributable tostacked individual layers; i.e., each layer is insufficient to provide adiffraction pattern, and it is only by stacking multiple phyllosilicatelayers that a diffraction pattern can be seen. In this case, thestacking appears to be extremely sensitive to trace intercalantimpurities which may exist between the phyllosilicate layers (e.g.,water), which influences the packing and therefor the location of thediffraction peak. Alternatively, different levels of silanol pendantsmay affect the stacking distances. In any case, the d-spacing of thestacked layers is in a range of from about 10.5 Å to about 11.5 Å.

The phyllosilicates also exhibit characteristic ²⁹Si and ¹H-²⁹Si CP MASNMR, as shown in FIGS. 26(A-B). Based on these MAS and CP-MAS spectra,the shifts, δ, at −113 ppm, −105 ppm, and −94 ppm correspond to Q⁴Si,Q³Si, and Q²Si show that 55% Q⁴Si and 45% Q³Si environments (Q4/Q3 ca.1:1). Given that the idealize structure shown in FIG. 23 would have66.7% Q⁴Si and 33.3% Q³Si environments (Q4/Q3=2:1).

Certain embodiments provide for the methods of making these materials.Other embodiments include those compositions which result from theapplication of these methods, to the extent that such compositionsdifferent from those described for the CIT-13P silicates.

These methods include those comprising treating a crystallinemicroporous CIT-5 or CIT-13 germanosilicate with a dilute aqueousmineral acid, at elevated temperatures, the crystalline microporousCIT-13 germanosilicate composition having an overall Si/Ge in a range offrom about 3.8 to about 4.35, 4.5, 5, 5.4, or 5.68. The resultingphyllosilicate CIT-13P can exhibit a Si/Ge ratio in a range of fromabout 40 to practically infinity, as described elsewhere herein. Thatis, in certain embodiments, the germania is practically completelyremoved; i.e., Si/Ge is practically infinity. In other embodiments, thetreatment provides compositions having detectable germania. In someembodiments, the treating is done at a temperature in a range of fromabout 80° C. to about 120° C., preferably at a time ranging from 12 to72 hours. Treatments done at about 100° C. for about 24 hours appear tobe sufficient to effect the transformation. In this context, the mineralacid comprises hydrochloric acid, nitric acid, phosphoric acid, and/orsulfuric acid, preferably comprising hydrochloric acid. The definitionof dilute mineral acid is as described elsewhere herein, though in thepresent context, concentrations in the range of 0.05 to about 0.3,preferably about 1 provides acceptable conversions (>65% based on theprecursor).

The CIT-13P silicates may also be characterized by their ability totransform to CIT-14 and CIT-15 germanosilicates, as described elsewhereherein.

Subsequent Reactions of the Phyllosilicate CIT-13P to Form Assembled andRe-Organized/Assembled Germanosilicate Compositions (CIT-14 and CIT-15)(Crystal Forms V and VI)

The phyllosilicate CIT-13P structures are also capable of topotacticrearrangements [(re)organizing and (re)assembling] to form newcrystalline microporous structures, designated CIT-14 and CIT-15 herein.Each of these CIT-14 and CIT-15 exhibits a high silica germanosilicateframework, having Si/Ge ratios ranging from about 25 to practicallyinfinity, including embodiments where this ratio is 75 to about 150 (inthe case of CIT-14) or about 50 to about 100 (in the case of CIT-15).Indeed, the overall transformation of the CIT-13 frameworks through thephyllosilicate intermediates to either or both of the CIT-14 and CIT-15frameworks, while practically retaining the original silica-richcfi-layers, is consistent with condensation and pillaringtransformations, sometimes referred to as ADOR(Assembly-Disassembly-Organization-Re-assembly).

B.1. Germanosilicate Compositions of CIT-15 Topology (Crystal Form V)

A first class of crystalline microporous silicates, designated CIT-15germanosilicates, may be obtained from CIT-13P phyllosilicates byapplying conditions consistent topotactic dehydration. Using suchmethods, crystalline microporous germanosilicate compositions of CIT-15topology have been characterized by the present inventors, and may bedefined in terms of PXRD patterns, and other analytical methods(including NMR).

Independent of the way in which these compounds can be prepared, incertain embodiments, the [CIT-15 germanosilicates (Form V) exhibit atleast one of:

(a) a powder X-ray diffraction (XRD) pattern exhibiting at least five ofthe characteristic peaks at 8.15±0.2, 10.13±0.2, 12.80±0.2, 16.35±0.2,19.03±0.2, 19.97±0.2, 20.33±0.2, 23.79±0.2, 23.91±0.2, 24.10±0.2,24.63±0.2, 25.77±0.2, 26.41±0.2, 27.75±0.2, 34.73±0.2, and 37.78±0.2degrees 2-θ;

(b) a powder X-ray diffraction (XRD) pattern substantially the same asshown in FIG. 27; or

(c) unit cell parameters substantially equal to those shown in Table 8.

TABLE 8 Cell parameters for CIT-15 germanosilicates Space group Cmmm a(Å) 17.4686(5) b (Å) 13.8271(2) c (Å) 5.1665(2) α = β = γ 90° SpaceGroup 65 (Cmmm)Note that the experimentally determine PXRD patterns show excellentcorrelation with those predicted theoretically, giving good evidence forthis characterization. The CIT-15 germanosilicates comprisethree-dimensional frameworks containing 10-MR channels. In someembodiments, these channels have dimensions of 5.6 Å×3.8 Å, variances ofthe metal or metalloid oxide content within these frameworks areexpected to affect these specific dimensions. FIG. 27.

In some embodiments, the crystalline CIT-15 germanosilicates have aSi/Ge ratio in a range of from 25 to infinity. When prepared fromCIT-13P phyllosilicate precursors, the Si/Ge ratio of the productgenerally reflects that of the precursor. In certain embodiments, then,the Si/Ge ratio can be described in terms of one or more ranges of from25 to 50, from 50 to 60, from 60 to 80, from 80 to 100, from 100 to 200,and from 200 to infinity, for example from 50 to 100.

The crystalline microporous CIT-15 germanosilicates can be prepared bycalcining the CIT-13P phyllosilicates. See FIG. 30. Other embodimentsinclude those compositions which result from the application of thesemethods, to the extent that such compositions different from thosedescribed for the CIT-15 germanosilicates. Calcining temperatures havebeen defined elsewhere herein, but in certain specific embodiments here,calcining includes subjecting the precursor material to at least onetemperature in a range of from about 400° C. to about 950° C. Goodresults have been achieved by calcining the CIT-13P at 580° C. to 750°C. for 6-8 hours. Topotactic condensations can occur with layeredmaterials that contain terminal silanol groups, such as CIT-13P. Withcalcination, these terminal silanol groups condense, releasing water andforming Si—O—Si bonds. In this process, a 2-dimensional material isconverted to a 3-dimensional framework material. Without intending to bebound by the correctness of any particular theory, the conversion ofCIT-13P phyllosilicates to crystalline microporous CIT-15germanosilicates is believed to be operating by this mechanism. E.g.,see FIG. 30. It has been shown to be helpful, but not necessary, tointercalate long chain (C₁₋₁₂) alkyl amines, for example 1-heptyl amineor 1-octyl amine with the CIT-13P phyllosilicates before calcining.Again, without intending to be bound by the correctness or anyparticular theory, it is believed that these amines help organize andsecure the positions of the pre-channels of the CIT-13P (e.g., as shownin the dotted circles of FIG. 30) before calcining.

B.2. Germanosilicate Compositions of CIT-14 Topology (Crystal Form VI)

A second class of crystalline microporous silicates, designated CIT-14germanosilicates, may be obtained from CIT-13P phyllosilicates byapplying conditions consistent with pillaring. In some embodiments,these crystalline microporous CIT-14 germanosilicates may be prepared byreacting CIT-13P phyllosilicates derived from CIT-13 germanosilicateshaving an Si/Ge ratio in a range of from 3.8 to about 5.68 with asilylating agent, in the presence of a concentrated mineral acid atelevated temperatures for times sufficient to effect the desiredtransformation. In the general context, the range of mineral acids isdescribed elsewhere herein, but in certain additional embodiments, themineral acid is or comprises nitric or hydrochloric acid, preferablynitric acid, in a concentration ranging from about 1 M to about 1.5 M,preferably 1.25 M. In certain embodiments, the reaction conditionsinclude contacting the CIT-13P with a source of silica, for example, asilylating agent, in the presence of the mineral acid at one or moretemperatures in a range of from about 165° C. to about 225° C.,preferably 175° C., under autogenous pressures for times ranging from 12to 36 hours, preferably from 18 to 24 hours, followed by calcination at580° C. to 750° C. for 6 to 10 hours. In specific embodiments, thesilylating agent comprises those known to be useful for pillaring suchstructures, for example including diethoxydimethylsilane (DEDMS) and/or1,3-diethoxy-1,1,3,3-tetramethyldisiloxane (DETMDS). In certainembodiments, the CIT-14 silicates have a Si/Ge ratio ranging from about25 to one approaching infinitity, if not infinity (i.e., pure silica).In other embodiments, the Si/Ge ratio is described as being in a rangeof from about 25 to 150, or from about 75 to about 150. RepresentativePXRD patterns, for a range of Si/Ge ratios, are illustrated in FIG. 31.

Independent of the way in which they were prepared, these new CIT-14germanosilicates exhibit powder X-ray diffraction (XRD) patterns havingat least five of the characteristic peaks at 7.7, 8.2, 13.1, 19.5, 21.1,22.7, and 27.6 degrees 2-θ. Owing to the structural disorder of thematerial, the observed diffraction peaks are broad, and the errorsassigned to these peaks are ±0.5 degrees 2-θ (see Table 9, FIGS. 31 and32). In other embodiments, the error associated with these peaks are±0.3 degrees 2-θ. Consistent with other structures prepared bypillaring, and with the methods by which they can be made, the structureof these new materials is described in terms of a three-dimensionalframeworks having pores defined by 8- and 12-membered rings. Based onthe theoretical structure, the 8- and 12-membered rings have dimensionsof 4.0×3.4 Å and 6.9×5.4 Å, respectively (see FIG. 33). The PXRDpatterns identified from isolated products are not identical, but areconsistent with the theoretical values associated with this structure(as predicted by the General Utility Lattice Program, GULP (Gale,1997)), i.e., having silica pillars separating the silica-richcfi-layers. See FIGS. 33 and 34. Again, such differences in the patternscan be explained by structural disorder and/or incomplete silicapillaring in the structure. In this case, versions of the CIT-14 mayalso be described in terms of the crystallographic parameters shown inFIGS. 33(A) and 33(B).

FIG. 35 shows a representative ²⁹Si MAS NMR showing small amounts of Q3Si species and multiple Q4 Si environments within the −108 to −120chemical shift regions.

TABLE 9 Comparison of Theoretical and actual values for PXRD patterns ofCIT-14 2-Theta Theoretical^(a) Example 1 Example 2 Example 3 Relative(Si/Ge = 4.4, (Si/Ge = 4.4, (Si/Ge = 3.8, 2-Theta Intensity DEDMS)DETDMS) DETDMS) 7.55 71.49 7.72 7.68 7.76 8.06 100 8.24 8.24 8.24 12.7911.78 13.08 13.04 13.12 18.82 31.01 19.4 19.4 19.5 119.04 17.96 — — —20.67 38.36 21.1 21.1 21.2 22.07 32.05 22.7 22.7 22.7 27.01 22.21 — — —27.48 11.35 27.6 27.6 27.6 ^(a)Based on structure shown in FIGS. 33(A-B)and 34.

TABLE 10 Compilation of Theoretical PXRD Data for CIT-13, CIT-14, andCIT-15 (from FIGS. 4, 33(A), and 27, respectively). CIT-13 CIT-14 CIT-15Germanosilicate Germanosilicate Germanosilicate Peak, Theoretical Peak,Theoretical Peak, Theoretical No. 2θ Intensity 2θ Intensity 2θ Intensity1 6.45 100 7.55 71.49 8.15 36.9 2 7.18 96.06 8.06 100 10.13 100 3 8.5613.58 8.58 7.57 12.80 44.7 4 10.73 9.51 11.44 7.61 16.35 50.67 5 11.1815.42 11.79 5.58 19.03 74.63 6 12.85 4.84 12.79 11.78 19.97 71.52 718.25 18.20 13.70 5.08 20.33 32.02 8 18.35 11.11 18.82 31.01 23.79 23.799 18.63 12.78 19.04 17.96 23.91 67.60 10 19.60 4.30 19.66 7.09 24.1041.49 11 20.78 16.13 20.67 38.36 24.63 22.41 12 21.55 9.61 22.07 32.0525.77 44.22 13 23.35 9.34 23.00 6.86 26.41 18.02 14 24.55 8.37 23.715.34 26.73 8.02 15 25.17 4.5 24.36 10.92 27.75 12.39 16 25.30 4.47 25.746.79 32.15 6.68 17 25.87 3.58 26.25 8.02 32.82 5.71 18 26.01 4.93 27.0122.21 34.73 16.07 19 26.68 14.48 27.48 11.35 35.39 6.49 20 33.99 3.7434.84 5.38 37.78 14.12Other Modifications to the Microcrystalline Compositions.

In certain of embodiments, the crystalline microporous solids describedin the present disclosure, including crystal Forms IA, IB, II, IIIA,IIIB, IV, V, and VI, are present in their hydrogen form. In otherembodiments, the crystalline microporous solids of Forms IA, IB, II,IIIA, IIIB, V, and VI containing at least one metal cation salt or atransition metal or salt in their micropores. In other specificembodiments, the metal cation salt is a salt of K⁺, Li⁺, Rb⁺, ca²⁺, Cs⁺:Co²⁺, Cu²⁺, Mg²⁺, Sr²⁺, Ba²⁺, Ni²⁺, or Fe²⁺, the copper salt mayinclude, for example, Schweizer's reagent (tetraamminediaquacopperdihydroxide, [Cu(NH₃)₄(H₂O)₂](OH)₂]), copper(II) nitrate, or copper(II)carbonate. Such metal cations may be incorporated, for example, usingtechniques known to be suitable for this purpose (e.g., ion exchange).

In other embodiments, the micropores may contain a transition metal ortransition metal oxide. The addition of such materials may beaccomplished, for example by chemical vapor deposition or chemicalprecipitation. In certain independent embodiments, the transition metalor transition metal oxide comprises an element of Groups 6, 7, 8, 9, 10,11, or 12. In other independent embodiments, the transition metal ortransition metal oxide comprises scandium, yttrium, titanium, zirconium,vanadium, manganese, chromium, molybdenum, tungsten, iron, ruthenium,osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper,silver, gold, or mixtures. Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag,Au, and mixtures thereof are preferred. In independent embodiments, theaqueous ammonium or metal salt or chemically vapor deposited orprecipitated materials independently include Li, Na, K, Rb, Cs, Be, Mg,Ca, Sr, Be, Al, Ga, In, Zn, Ag, Cd, Ru, Rh, Pd, Pt, Au, Hg, La, Ce, Pr,Nd, Pm, Sm, Eu, or R_(4-n)N⁺H_(n) cations, where R is alkyl, n=0-4 in atleast some of its pores.

The term “transition metal” have been defined elsewhere herein, but incertain other independent embodiments, the transition metal ortransition metal oxide comprises an element of Groups 6, 7, 8, 9, 10,11, or 12. In still other independent embodiments, the transition metalor transition metal oxide comprises scandium, yttrium, titanium,zirconium, vanadium, manganese, chromium, molybdenum, tungsten, iron,ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium,platinum, copper, silver, gold, or mixtures. Fe, Ru, Os, Co, Rh, Ir, Ni,Pd, Pt, Cu, Ag, Au, and mixtures thereof are preferred dopants.

In other embodiments, the optionally doped crystalline solids arecalcined in air a temperature defined as being in at least one range offrom 400° C. to 500° C., from 500° C. to 600° C., from 600° C. to 700°C., from 700° C. to 800° C., from 800° C. to 900° C., from 900° C. to1000° C., from 1000° C. to 1200° C., 500° C. to about 1200° C. Thechoice of any particular temperature may, in some cases, be limited bythe stability of the particular solid, either with respect todecomposition or onward conversion to another crystal phase.

Other methods for modifying molecular sieves for use as catalysts areknown by those skilled in the art, and any such additional modificationsare considered within the scope of this disclosure

Uses of the Inventive Compositions—Catalytic Transformations

In various embodiments, the crystalline microporous germanosilicatesolids of the present invention, calcined, doped, or treated asdescribed herein, act as catalysts to mediate or catalyze an array ofchemical transformation. All such combinations of compositions andcatalytic reactions are considered individual embodiments of thisdisclosure, as if they have been individually and separately delineated.Such transformations may include carbonylating DME with CO at lowtemperatures, reducing NOx with methane (e.g., in exhaust applications),cracking, hydrocracking, dehydrogenating, converting paraffins toaromatics, dewaxing a hydrocarbon feedstock, MTO, isomerizing aromatics(e.g., xylenes), disproportionating aromatics (e.g., toluene),alkylating aromatic hydrocarbons, oligomerizing alkenes, aminating loweralcohols, separating and sorbing lower alkanes, hydrocracking ahydrocarbon, dewaxing a hydrocarbon feedstock, isomerizing an olefin,producing a higher molecular weight hydrocarbon from lower molecularweight hydrocarbon, reforming a hydrocarbon, converting lower alcohol orother oxygenated hydrocarbons to produce olefin products, epoxidingolefins with hydrogen peroxide, reducing the content of an oxide ofnitrogen contained in a gas stream in the presence of oxygen, orseparating nitrogen from a nitrogen-containing gas mixture by contactingthe respective feedstock with the a catalyst comprising the crystallinemicroporous solid of any one of materials described herein underconditions sufficient to affect the named transformation. Particularlyattractive applications include in which these germanosilicates areexpected to be useful include catalytic cracking, hydrocracking,dewaxing, alkylation, and olefin and aromatics formation reactions.Additional applications include gas drying and separation.

Specific embodiments provide hydrocracking processes, each processcomprising contacting a hydrocarbon feedstock under hydrocrackingconditions with a catalyst comprising a crystalline microporous solid ofthis invention, preferably predominantly in the hydrogen form.

Still other embodiments provide processes for dewaxing hydrocarbonfeedstocks, each process comprising contacting a hydrocarbon feedstockunder dewaxing conditions with a catalyst comprising a crystallinemicroporous solid of this invention. Yet other embodiments provideprocesses for improving the viscosity index of a dewaxed product of waxyhydrocarbon feeds, each process comprising contacting the waxyhydrocarbon feed under isomerization dewaxing conditions with a catalystcomprising a crystalline microporous solid of this invention.

Additional embodiments include those process for producing a C20+ lubeoil from a C20+ olefin feed, each process comprising isomerizing saidolefin feed under isomerization conditions over a catalyst comprising atleast one transition metal catalyst and a crystalline microporous solidof this invention.

Also included in the present invention are processes for isomerizationdewaxing a raffinate, each process comprising contacting said raffinate,for example a bright stock, in the presence of added hydrogen with acatalyst comprising at least one transition metal and a crystallinemicroporous solid of this invention.

Other embodiments provide for dewaxing a hydrocarbon oil feedstockboiling above about 350° F. and containing straight chain and slightlybranched chain hydrocarbons comprising contacting said hydrocarbon oilfeedstock in the presence of added hydrogen gas at a hydrogen pressureof about 15-3000 psi with a catalyst comprising at least one transitionmetal and a crystalline microporous solid of this invention, preferablypredominantly in the hydrogen form.

Also included in the present invention is a process for preparing alubricating oil which comprises hydrocracking in a hydrocracking zone ahydrocarbonaceous feedstock to obtain an effluent comprising ahydrocracked oil, and catalytically dewaxing said effluent comprisinghydrocracked oil at a temperature of at least about 400° F. and at apressure of from about 15 psig to about 3000 psig in the presence ofadded hydrogen gas with a catalyst comprising at least one transitionmetal and a crystalline microporous solid of this invention.

Also included in this invention is a process for increasing the octaneof a hydrocarbon feedstock to produce a product having an increasedaromatics content, each process comprising contacting ahydrocarbonaceous feedstock which comprises normal and slightly branchedhydrocarbons having a boiling range above about 40° C. and less thanabout 200° C., under aromatic conversion conditions with a catalystcomprising a crystalline microporous solid of this invention. In theseembodiments, the crystalline microporous solid is preferably madesubstantially free of acidity by neutralizing said solid with a basicmetal. Also provided in this invention is such a process wherein thecrystalline microporous solid contains a transition metal component.

Also provided by the present invention are catalytic cracking processes,each process comprising contacting a hydrocarbon feedstock in a reactionzone under catalytic cracking conditions in the absence of addedhydrogen with a catalyst comprising a crystalline microporous solid ofthis invention. Also included in this invention is such a catalyticcracking process wherein the catalyst additionally comprises anadditional large pore crystalline cracking component.

This invention further provides isomerization processes for isomerizingC4 to C7 hydrocarbons, each process comprising contacting a feed havingnormal and slightly branched C4 to C hydrocarbons under isomerizingconditions with a catalyst comprising a crystalline microporous solid ofthis invention, preferably predominantly in the hydrogen form. Thecrystalline microporous solid may be impregnated with at least onetransition metal, preferably platinum. The catalyst may be calcined in asteam/air mixture at an elevated temperature after impregnation of thetransition metal.

Also provided by the present invention are processes for alkylating anaromatic hydrocarbon, each process comprising contacting underalkylation conditions at least a molar excess of an aromatic hydrocarbonwith a C2 to C20 olefin under at least partial liquid phase conditionsand in the presence of a catalyst comprising a crystalline microporoussolid of this invention, preferably predominantly in the hydrogen form.The olefin may be a C2 to C4 olefin, and the aromatic hydrocarbon andolefin may be present in a molar ratio of about 4:1 to about 20:1,respectively. The aromatic hydrocarbon may be selected from the groupconsisting of benzene, toluene, ethylbenzene, xylene, or mixturesthereof.

Further provided in accordance with this invention are processes fortransalkylating an aromatic hydrocarbon, each of which process comprisescontacting under transalkylating conditions an aromatic hydrocarbon witha polyalkyl aromatic hydrocarbon under at least partial liquid phaseconditions and in the presence of a catalyst comprising a crystallinemicroporous solid of this invention, preferably predominantly in thehydrogen form. The aromatic hydrocarbon and the polyalkyl aromatichydrocarbon may be present in a molar ratio of from about 1:1 to about25:1, respectively. The aromatic hydrocarbon may be selected from thegroup consisting of benzene, toluene, ethylbenzene, xylene, or mixturesthereof, and the polyalkyl aromatic hydrocarbon may be a dialkylbenzene.

Further provided by this invention are processes to convert paraffins toaromatics, each of which process comprises contacting paraffins underconditions which cause paraffins to convert to aromatics with a catalystcomprising a crystalline microporous solid of this invention, saidcatalyst comprising gallium, zinc, or a compound of gallium or zinc.

In accordance with this invention there is also provided processes forisomerizing olefins, each process comprising contacting said olefinunder conditions which cause isomerization of the olefin with a catalystcomprising a crystalline microporous solid of this invention.

Further provided in accordance with this invention are processes forisomerizing an isomerization feed, each process comprising an aromaticC8 stream of xylene isomers or mixtures of xylene isomers andethylbenzene, wherein a more nearly equilibrium ratio of ortho-, meta-and para-xylenes is obtained, said process comprising contacting saidfeed under isomerization conditions with a catalyst comprising acrystalline microporous solid of this invention.

The present invention further provides processes for oligomerizingolefins, each process comprising contacting an olefin feed underoligomerization conditions with a catalyst comprising a crystallinemicroporous solid of this invention.

This invention also provides processes for converting lower alcohols andother oxygenated hydrocarbons, each process comprising contacting saidlower alcohol (for example, methanol, ethanol, or propanol) or otheroxygenated hydrocarbon with a catalyst comprising a crystallinemicroporous solid of this invention under conditions to produce liquidproducts.

Also provided by the present invention are processes for reducing oxidesof nitrogen contained in a gas stream in the presence of oxygen whereineach process comprises contacting the gas stream with a crystallinemicroporous solid of this invention. The a crystalline microporous solidmay contain a metal or metal ions (such as cobalt, copper or mixturesthereof) capable of catalyzing the reduction of the oxides of nitrogen,and may be conducted in the presence of a stoichiometric excess ofoxygen. In a preferred embodiment, the gas stream is the exhaust streamof an internal combustion engine.

Also provided are processes for converting synthesis gas containinghydrogen and carbon monoxide, also referred to as syngas or synthesisgas, to liquid hydrocarbon fuels, using a catalyst comprising any of thegermanosilicates described herein, including those having CIT-13frameworks, and Fischer-Tropsch catalysts. Such catalysts are describedin U.S. Pat. No. 9,278,344, which is incorporated by reference for itsteaching of the catalysts and methods of using the catalysts. TheFischer-Tropsch component includes a transition metal component ofgroups 8-10 (i.e., Fe, Ru, Os, Co, Rh, IR, Ni, Pd, Pt), preferablycobalt, iron and/or ruthenium. The optimum amount of catalyticallyactive metal present depends inter alia on the specific catalyticallyactive metal. Typically, the amount of cobalt present in the catalystmay range from 1 to 100 parts by weight per 100 parts by weight ofsupport material, preferably from 10 to 50 parts by weight per 100 partsby weight of support material. In one embodiment, from 15 to 45 wt %cobalt is deposited on the hybrid support as the Fischer-Tropschcomponent. In another embodiment from 20 to 45 wt % cobalt is depositedon the hybrid support. The catalytically active Fischer-Tropschcomponent may be present in the catalyst together with one or more metalpromoters or co-catalysts. The promoters may be present as metals or asmetal oxide, depending upon the particular promoter concerned. Suitablepromoters include metals or oxides of transition metals, includinglanthanides and/or the actinides or oxides of the lanthanides and/or theactinides. As an alternative or in addition to the metal oxide promoter,the catalyst may comprise a metal promoter selected from Groups 7 (Mn,Tc, Re) and/or Groups 8-10. In some embodiments, the Fischer-Tropschcomponent further comprises a cobalt reduction promoter selected fromthe group consisting of platinum, ruthenium, rhenium, silver andcombinations thereof. The method employed to deposit the Fischer-Tropschcomponent on the hybrid support involves an impregnation technique usingaqueous or non-aqueous solution containing a soluble cobalt salt and, ifdesired, a soluble promoter metal salt, e.g., platinum salt, in order toachieve the necessary metal loading and distribution required to providea highly selective and active hybrid synthesis gas conversion catalyst.

Still further process embodiments include those for reducing halideconcentration in an initial hydrocarbon product comprising undesirablelevels of an organic halide, the process comprising contacting at leasta portion of the hydrocarbon product with a composition comprising anyof the germanosilicate structures described herein, including CIT-13,under organic halide absorption conditions to reduce the halogenconcentration in the hydrocarbon. The initial hydrocarbon product may bemade by a hydrocarbon conversion process using an ionic liquid catalystcomprising a halogen-containing acidic ionic liquid. In someembodiments, the organic halid content in the initial hydrocarbonproduct is in a range of from 50 to 4000 ppm; in other embodiments, thehalogen concentrations are reduced to provide a product having less than40 ppm. In other embodiments, the production may realize a reduction of85%, 90%, 95%, 97%, or more. The initial hydrocarbon stream may comprisean alkylate or gasoline alkylate. Preferably the hydrocarbon alkylate oralkylate gasoline product is not degraded during the contacting. Any ofthe materials or process conditions described in U.S. Pat. No. 8,105,481are considered to describe the range of materials and process conditionsof the present invention. U.S. Pat. No. 8,105,481 is incorporated byreference at least for its teachings of the methods and materials usedto effect such transformations (both alkylations and halogenreductions).

Still further process embodiments include those processes for increasingthe octane of a hydrocarbon feedstock to produce a product having anincreased aromatics content comprising contacting a hydrocarbonaceousfeedstock which comprises normal and slightly branched hydrocarbonshaving a boiling range above about 40 C and less than about 200 C underaromatic conversion conditions with the catalyst.

Specific conditions for many of these transformations are known to thoseof ordinary skill in the art. Exemplary conditions for suchreactions/transformations may also be found in WO/1999/008961, U.S. Pat.Nos. 4,544,538, 7,083,714, 6,841,063, and 6,827,843, each of which areincorporated by reference herein in its entirety for at least thesepurposes.

Depending upon the type of reaction which is catalyzed, the microporoussolid may be predominantly in the hydrogen form, partially acidic orsubstantially free of acidity. The skilled artisan would be able todefine these conditions without undue effort. As used herein,“predominantly in the hydrogen form” means that, after calcination(which may also include exchange of the pre-calcined material with NH₄ ⁺prior to calcination), at least 80% of the cation sites are occupied byhydrogen ions and/or rare earth ions.

The germanosilicates of the present invention may also be used asadsorbents for gas separations. For example, these germanosilicate canalso be used as hydrocarbon traps, for example, as a cold starthydrocarbon trap in combustion engine pollution control systems. Inparticular, such germanosilicate may be particularly useful for trappingC₃ fragments. Such embodiments may comprise processes and devices fortrapping low molecular weight hydrocarbons from an incoming gas stream,the process comprising passing the gas stream across or through acomposition comprising any one of the crystalline microporousgermanosilicate compositions described herein, so as to provide anoutgoing gas stream having a reduced concentration of low molecularweight hydrocarbons relative to the incoming gas stream. In thiscontext, the term “low molecular weight hydrocarbons” refers to C1-C6hydrocarbons or hydrocarbon fragments.

The germanosilicates of the present invention may also be used in aprocess for treating a cold-start engine exhaust gas stream containinghydrocarbons and other pollutants, wherein the process comprises orconsist of flowing the engine exhaust gas stream over one of thegermanosilicate compositions of the present invention whichpreferentially adsorbs the hydrocarbons over water to provide a firstexhaust stream, and flowing the first exhaust gas stream over a catalystto convert any residual hydrocarbons and other pollutants contained inthe first exhaust gas stream to innocuous products and provide a treatedexhaust stream and discharging the treated exhaust stream into theatmosphere.

The germanosilicates of the present invention can also be used toseparate gases. For example, these can be used to separate water, carbondioxide, and sulfur dioxide from fluid streams, such as low-gradenatural gas streams, and carbon dioxide from natural gas. Typically, themolecular sieve is used as a component in a membrane that is used toseparate the gases. Examples of such membranes are disclosed in U.S.Pat. No. 6,508,860.

For each of the preceding processes described, additional correspondingembodiments include those comprising a device or system comprising orcontaining the materials described for each process. For example, in thegas of the gas trapping, additional embodiments include those devicesknown in the art as hydrocarbon traps which may be positioned in theexhaust gas passage of a vehicle. In such devices, hydrocarbons areadsorbed on the trap and stored until the engine and exhaust reach asufficient temperature for desorption. The devices may also comprisemembranes comprising the germanosilicate compositions, useful in theprocesses described.

Terms

In the present disclosure the singular forms “a,” “an,” and “the”include the plural reference, and reference to a particular numericalvalue includes at least that particular value, unless the contextclearly indicates otherwise. Thus, for example, a reference to “amaterial” is a reference to at least one of such materials andequivalents thereof known to those skilled in the art, and so forth.

When a value is expressed as an approximation by use of the descriptor“about,” it will be understood that the particular value forms anotherembodiment. In general, use of the term “about” indicates approximationsthat can vary depending on the desired properties sought to be obtainedby the disclosed subject matter and is to be interpreted in the specificcontext in which it is used, based on its function. The person skilledin the art will be able to interpret this as a matter of routine. Insome cases, the number of significant figures used for a particularvalue may be one non-limiting method of determining the extent of theword “about.” In other cases, the gradations used in a series of valuesmay be used to determine the intended range available to the term“about” for each value. Where present, all ranges are inclusive andcombinable. That is, references to values stated in ranges include everyvalue within that range.

It is to be appreciated that certain features of the invention whichare, for clarity, described herein in the context of separateembodiments, may also be provided in combination in a single embodiment.That is, unless obviously incompatible or specifically excluded, eachindividual embodiment is deemed to be combinable with any otherembodiment(s) and such a combination is considered to be anotherembodiment. Conversely, various features of the invention that are, forbrevity, described in the context of a single embodiment, may also beprovided separately or in any sub-combination. Finally, while anembodiment may be described as part of a series of steps or part of amore general structure, each said step may also be considered anindependent embodiment in itself, combinable with others.

The transitional terms “comprising,” “consisting essentially of” and“consisting” are intended to connote their generally in acceptedmeanings in the patent vernacular; that is, (i) “comprising,” which issynonymous with “including,” “containing,” or “characterized by,” isinclusive or open-ended and does not exclude additional, unrecitedelements or method steps; (ii) “consisting of” excludes any element,step, or ingredient not specified in the claim; and (iii) “consistingessentially of” limits the scope of a claim to the specified materialsor steps “and those that do not materially affect the basic and novelcharacteristic(s)” of the claimed invention. Embodiments described interms of the phrase “comprising” (or its equivalents), also provide, asembodiments, those which are independently described in terms of“consisting of” and “consisting essentially of” For those embodimentsprovided in terms of “consisting essentially of” the basic and novelcharacteristic(s) is the facile operability of the methods orcompositions/systems to provide the germanosilicate compositions atmeaningful yields or the ability of the systems using only thoseingredients listed.

The term “meaningful product yields” is intended to reflect productyields such as described herein, but also including greater than 20%,but when specified, this term may also refer to yields of 10%, 20%, 30%,40%, 50%, 60%, 70%, 80%, or 90% or more, relative to the amount oforiginal substrate.

When a list is presented, unless stated otherwise, it is to beunderstood that each individual element of that list, and everycombination of that list, is a separate embodiment. For example, a listof embodiments presented as “A, B, or C” is to be interpreted asincluding the embodiments, “A,” “B,” “C,” “A or B,” “A or C,” “B or C,”or “A, B, or C,” as separate embodiments, as well as C₁₋₃.

Throughout this specification, words are to be afforded their normalmeaning, as would be understood by those skilled in the relevant art.However, so as to avoid misunderstanding, the meanings of certain termswill be specifically defined or clarified.

The term “alkyl” as used herein refers to a linear, branched, or cyclicsaturated hydrocarbon group typically although not necessarilycontaining 1 to about 6 carbon atoms, such as methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, tert-butyl, and the like.

The term “aromatic” refers to the ring moieties which satisfy the Hückel4n+2 rule for aromaticity, and includes both aryl (i.e., carbocyclic)and heteroaryl structures.

The term “halide” is used in the conventional sense to refer to achloride, bromide, fluoride, or iodide.

“Lower alcohols” or lower alkanes refer to alcohols or alkanes,respectively, having 1-10 carbons, linear or branched, preferably 1-6carbon atoms and preferably linear. Methanol, ethanol, propanol,butanol, pentanol, and hexanol are examples of lower alcohols. Methane,ethane, propane, butane, pentane, and hexane are examples of loweralkanes.

As used herein, unless otherwise specified, the term “elevatedtemperatures” typically refers to at least one temperature in a range offrom about 170° C. to about 230° C. The term “calcining” is reserved forhigher temperatures. Unless otherwise specified, it refers to one ormore temperatures in a range of from about 450° C. to about 1200° C. Theterm “delaminating temperature is intended to connote a temperature lessthan about 150° C., preferably in a range of from about 80° C. to about120° C.

As used herein, the terms “metals or metalloids,” as in “sources ofmetals or metalloids” or “oxides of metals or metalloids,” refers tothose Group 4, 5, 8, 13, 14, and 15 elements of the Periodic Table.These elements are typically found as oxides in molecular sieves,including for example, aluminum, boron, gallium, hafnium, iron, silicon,tin, titanium, vanadium, zinc, zirconium, or combinations thereof.

Typical sources of silicon oxide for the reaction mixtures includealkoxides, hydroxides, or oxides of silicon, or combination thereof.Exemplary compounds also include silicates (including sodium silicate),silica hydrogel, silicic acid, fumed silica, colloidal silica,tetra-alkyl orthosilicates, silica hydroxides, or combination thereof.Sodium silicate or tetraorthosilicates, for example tetraethylorthosilicate (TEOS), diethoxydimethylsilane (DEDMS) and/or1,3-diethoxy-1,1,3,3-tetramethyldisiloxane (DETMDS) are preferredsources.

Sources of germanium oxide can include alkali metal orthogermanates,M₄GeO₄, containing discrete GeO₄ ⁴⁻ ions, GeO(OH)₃ ⁻, GeO₂(OH)₂ ²⁻,[(Ge(OH)₄)₈(OH)₃]³⁻ or neutral solutions of germanium dioxide containGe(OH)₄, or alkoxide or carboxylate derivatives thereof.

Typical sources of aluminum oxide for the reaction mixture includealuminates, alumina, aluminum colloids, aluminum alkoxides, aluminumoxide coated on silica sol, hydrated alumina gels such as Al(OH)₃ and asodium aluminate. Sources of aluminum oxide may also comprise analkoxide, hydroxide, or oxide of aluminum, or combination thereof.Additionally, the sources of alumina may also comprise other ligands aswell, for example acetylacetonate, carboxylates, and oxalates; suchcompounds are well known as useful in hydrothermal or sol-gel syntheses.Additional sources of aluminum oxide can include aluminum salts, such asAlCl₃, Al(OH)₃, Al(NO₃)₃, and Al₂(SO₄)₃,

Sources of boron oxide, gallium oxide, hafnium oxide, iron oxide, tinoxide, titanium oxide, indium oxide, vanadium oxide, and/or zirconiumoxide can be added in forms corresponding to their aluminum and siliconcounterparts.

As used herein, the term “mineral acids” refer to mineralizing acidsconventionally used in molecular sieve zeolite syntheses, for exampleHCl, HBr, HF, HNO₃, or H₂SO₄. Oxalic acid and other strong organic acidsmay also be employed in lieu of mineral acids. Generally, HCl and HNO₃are preferred mineral acids. As used herein throughout, the terms“concentrated” and “dilute” with respect to mineral acids refers toconcentrations in excess and less than 0.5 M, respectively. In someembodiments, the term “concentrated” refers to concentrations in one ormore of a range from 0.5 to 0.6, from 0.6 to 0.7, from 0.7 to 0.8, from0.8 to 0.9, from 0.9 to 1.0, from 1.0 to 1.1, from 1.1 to 1.2, from 1.2to 1.3, from 1.3 to 1.4, from 1.4 to 1.5, from 1.5 to 1.6, from 1.6 to1.7, from 1.7 to 1.8, from 1.8 to 1.9, and from 1.9 to 2.0 or higher. Inexperiments described herein, and in preferred embodiments, concentratedacids refer to those in a composition range of from 0.9 to 1.1 M.Similarly, the term “dilute” refers to concentrations in one or more ofa range from 0.5 to 0.4, from 0.4 to 0.3, from 0.3 to 0.2, from 0.2 to0.15, from 0.15 to 0.1, and from 0.1 to 0.05. In experiments describedherein, and in preferred embodiments, dilute acids refer to those in acomposition range of from 0.5 to 0.15 M.

The term “CIT-5” topology describes a crystalline composition analogousto that described in U.S. Pat. Nos. 6,040,258 and 6,043,179, having aset of one-dimensional extra-large 14-MR pores. Pure silicate andaluminosilicate CIT-5 materials are prepared using very expensiveOrganic Structure Directing Agent (−)-N-methylsparteinium hydroxide. SeeWagner, P., et al., Chem. Comm., 1997m 217902180. The term “CIT-13”topology describes a crystalline microporous composition analogous tothat described in U.S. patent application Ser. No. 15/169,816, having aset of orthogonally oriented 14-membered pores. The term“phyllosilicate” refers to a 2-dimensional layered structure ofsilica-containing oxides.

The terms “oxygenated hydrocarbons” or “oxygenates” as known in the artof hydrocarbon processing to refer to components which include alcohols,aldehydes, carboxylic acids, ethers, and/or ketones which are known tobe present in hydrocarbon streams or derived from biomass streams othersources (e.g. ethanol from fermenting sugar).

The terms “separating” or “separated” carry their ordinary meaning aswould be understood by the skilled artisan, insofar as they connotephysically partitioning or isolating solid product materials from otherstarting materials or co-products or side-products (impurities)associated with the reaction conditions yielding the material. As such,it infers that the skilled artisan at least recognizes the existence ofthe product and takes specific action to separate or isolate it fromstarting materials and/or side- or byproducts. Absolute purity is notrequired, though it is preferred. In the case where the terms are usedin the context of gas processing, the terms “separating” or “separated”connote a partitioning of the gases by adsorption or by permeation basedon size or physical or chemical properties, as would be understood bythose skilled in the art.

Unless otherwise indicated, the term “isolated” means physicallyseparated from the other components so as to be free of at leastsolvents or other impurities, such as starting materials, co-products,or byproducts. In some embodiments, the isolated crystalline materials,for example, may be considered isolated when separated from the reactionmixture giving rise to their preparation, from mixed phase co-products,or both. In some of these embodiments, pure germanosilicates (includingstructures with or without incorporated OSDAs) can be made directly fromthe described methods. In some cases, it may not be possible to separatecrystalline phases from one another, in which case, the term “isolated”can refer to separation from their source compositions.

The term “microporous,” according to IUPAC notation refers to a materialhaving pore diameters of less than 2 nm. Similarly, the term“macroporous” refers to materials having pore diameters of greater than50 nm. And the term “mesoporous” refers to materials whose pore sizesare intermediate between microporous and macroporous. Within the contextof the present disclosure, the material properties and applicationsdepend on the properties of the framework such as pore size anddimensionality, cage dimensions and material composition. Due to thisthere is often only a single framework and composition that givesoptimal performance in a desired application.

“Optional” or “optionally” means that the subsequently describedcircumstance may or may not occur, so that the description includesinstances where the circumstance occurs and instances where it does not.For example, the phrase “optionally substituted” means that anon-hydrogen substituent may or may not be present on a given atom, and,thus, the description includes structures wherein a non-hydrogensubstituent is present and structures wherein a non-hydrogen substituentis not present.

The terms “method(s)” and “process(es)” are considered interchangeablewithin this disclosure.

As used herein, the term “crystalline microporous solids” or“crystalline microporous germanosilicate” are crystalline structureshaving very regular pore structures of molecular dimensions, i.e., under2 nm. The maximum size of the species that can enter the pores of acrystalline microporous solid is controlled by the dimensions of thechannels. These terms may also refer specifically to CIT-13compositions.

As used herein, the term “pillaring” refers generally to a process thatintroduces stable metal oxide structures (“so-called “pillars”) betweensubstantially parallel crystalline silicate layers. The metal oxidestructures keep the silicate layers separated, creating by interlayerspacings of molecular dimensions. The term is generally used in thecontext of clay chemistry and are well understood by those skilled inthe art of clays and zeolites, especially as applied to catalysts.

The term “silicate” refers to any composition including silicate (orsilicon oxide) within its framework. It is a general term encompassing,for example, pure-silica (i.e., absent other detectable metal oxideswithin the framework), aluminosilicate, borosilicate, ferrosilicate,germanosilicate, stannosilicate, titanosilicate, or zincosilicatestructures. The term “germanosilicate” refers to any compositionincluding silicon and germanium oxides within its framework. The term“pure,” such as “pure silicate” or “pure germanosilicate,” connote thatthese compositions contain, as far as practicably possible, only silicaor germania and silica, respectively, and any other metal oxides withinthe framework are present as inevitable, unintended, impurities. Thegermanosilicate may be “pure-germanosilicate” or optionally substitutedwith other metal or metalloid oxides. Likewise, the termsaluminosilicate, borosilicate, ferrosilicate, stannosilicate,titanosilicate, or zincosilicate structures are those containing siliconoxides and oxides of aluminum, boron, iron, tin, titanium, and zinc,respectively. When described as “optionally substituted,” the respectiveframework may contain aluminum, boron, gallium, germanium, hafnium,iron, tin, titanium, indium, vanadium, zinc, zirconium, or other atomsor oxides substituted for one or more of the atoms or oxides not alreadycontained in the parent framework.

As used herein, the term “transition metal” refers to any element in thed-block of the Periodic Table, which includes groups 3 to 12 on thePeriodic Table. In actual practice, the f-block lanthanide and actinideseries are also considered transition metals and are called “innertransition metals. This definition of transition metals also encompassesGroup 3 to Group 12 elements. In certain other independent embodiments,the transition metal or transition metal oxide comprises an element ofGroups 6, 7, 8, 9, 10, 11, or 12. In still other independentembodiments, the transition metal or transition metal oxide comprisesscandium, yttrium, titanium, zirconium, vanadium, manganese, chromium,molybdenum, tungsten, iron, ruthenium, osmium, cobalt, rhodium, iridium,nickel, palladium, platinum, copper, silver, gold, or mixtures. Fe, Ru,Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, and mixtures thereof arepreferred dopants.

The following listing of Embodiments is intended to complement, ratherthan displace or supersede, the previous descriptions.

Embodiment 1

A crystalline silicate composition derived or derivable from at leastone transformation of a crystalline microporous, optionallyhydrothermally derived, CIT-13 germanosilicate. In Aspects of thisEmbodiment, the crystalline silicate composition is the product of thereaction(s) attributed to them. In other Aspects of this Embodiment, thecrystalline silicate is independent of the methods described as used toprepare them (i.e., they may be produced by any other means. In someAspects of this Embodiment, the CIT-13 germanosilicate has a Si/Ge ratioin a range of from 3.8 to 10. In other Aspects, the optionallyhydrothermally derived CIT-13 germanosilicate is one described in U.S.patent application Ser. No. 15/169,816. As described herein, the CIT-13germanosilicate comprises silica-rich cfi-layers joined and spatiallyseparated by germani-rich D4R units, the latter being subject tomodifications under the conditions described herein. In separate Aspectsof this Embodiment, the term transformation refers to degermanation ofthe CIT-13 structures and to the topotactic rearrangement of thegermania D4R units. In some Aspects of this Embodiment, the crystallinecomposition is microporous; in other Aspects, it is not.

Embodiment 2

The crystalline silicate composition of Embodiment 1, further comprisingat least one oxide of a metal or metalloid, M, where M is aluminum,boron, gallium, hafnium, iron, tin, titanium, vanadium, zinc, orzirconium. In preferred Aspects of this Embodiment, M is aluminum. Incertain Aspects of this Embodiment, the at least one oxide is present inthe crystalline silicate composition at levels consistent with those ofthe precursor crystalline microporous, optionally hydrothermallyderived, CIT-13 germanosilicate (i.e., the Si/M ratios are the same orsimilar). In other Aspects of this Embodiment, the at least one oxide ispresent in the crystalline silicate composition is enriched relative tothose of the precursor crystalline microporous, optionallyhydrothermally derived, CIT-13 germanosilicate (i.e., the Si/M ratios atleast two times higher in the latter than in the former).

Embodiment 3

The crystalline silicate composition of Embodiment 1 or 2, that ismicroporous and the result of degermanating the crystalline microporous,optionally hydrothermally derived, CIT-13 germanosilicate.

Embodiment 4

The crystalline silicate composition of any one of Embodiments 1 to 3,that is microporous, having a Si/Ge ratio in a range of from about 25 toabout 200. In certain Aspects of this Embodiment, the Si/Ge ratio is ina range from about 25 to about 50, from 50 to about 100, from about 100to about 125, from about 125 to about 150, from about 150 to about 200,from about 200 to about 250, from about 250 to about 500, from 500 toinfinity, or any combination of two or more of these ranges. In certainAspects of this Embodiment, the composition is one that has beenprepared by the reaction of a concentrated mineral acid with asilica-rich CIT-13 germanosilicate having a Si/Ge ratio in a range offrom about 4.5 to about 10, under conditions described herein for thisconversion. In still other Aspects of this Embodiment, the compositionexhibits a PXRD patter having peaks associated with the (200) and (110)crystallographic planes as described in FIG. 7

Embodiment 5

The crystalline silicate composition of Embodiment 4 further comprisingat least one oxide of a metal or metalloid, M, where M is aluminum,boron, gallium, hafnium, iron, silicon, tin, titanium, vanadium, zinc,or zirconium, in a Si/M ratio in a range from about 25 to about 250. Incertain Aspects of this Embodiment, the Si/M ratio is in range fromabout 25 to about 50, from 50 to about 100, from about 100 to about 125,from about 125 to about 150, from about 150 to about 200, from about 200to about 250, from about 250 to about 500, from 500 to infinity, or anycombination of two or more of these ranges. In certain Aspects of thisEmbodiment, the composition is one that has been prepared by thereaction of a concentrated mineral acid and a source of the metal ormetalloid oxide with a silica-rich CIT-13 germanosilicate having a Si/Geratio in a range of from about 4.5 to about 10, under conditionsdescribed herein for this conversion. In other Aspects of thisEmbodiment, the crystalline silicate composition may be characterized ashaving silica-rich cfi-layers connected by units comprising at least oneoxide of aluminum, boron, gallium, hafnium, iron, silicon, tin,titanium, vanadium, zinc, or zirconium.

Embodiment 6

The crystalline silicate composition of any one of Embodiments 1 to 5that is a microporous aluminosilicate.

Embodiment 7

The crystalline silicate composition of Embodiment 5 or 6 that exhibitsa ²⁷Al MAS NMR spectrum having a characteristic chemical shift at about54.1 ppm, relative to 1 M aqueous aluminum nitrate solution,corresponding to tetrahedral Al sites. In further Aspects of thisEmbodiment, the aluminosilicate further exhibits chemical shifts at orabout 64.7 ppm and/or at or about 47.0 ppm, for example as shown in FIG.10, corresponding to additional tetrahedral sites, and optionallychemical shifts at or about 6.7, 0.5, −1.1, and/or −7.1 ppm,corresponding to octahedral sites.

Embodiment 8

The crystalline silicate composition of any one of Embodiments 5 to 7that exhibits a ²⁹Si MAS NMR spectrum having characteristic chemicalshifts at about −110 ppm and −115 ppm, relative to tetramethylsilane(TMS). In certain Aspects of this Embodiment, the ²⁹Si MAS NMR spectrumcontains the features as shown in FIGS. 11(A-B).

Embodiment 9

The crystalline silicate composition of Embodiment 1 or 2, whichcomprises a crystalline microporous germanosilicate composition havingCIT-5 topology and a Si/Ge ratio in a range of from about 3.8 to about5. In certain Aspects of this Embodiment, the Si/Ge ratio is in at leastone of the ranges of from about 3.8 to about 4, from about 4 to about4.2, from about 4.2 to about 4.4, from about 4.4 to about 4.6, fromabout 4.6 to about 4.8, or from about 4.8 to about 5.

Embodiment 10

The crystalline silicate composition of Embodiment 9, wherein thecrystalline microporous CIT-5 germanosilicate is derived from thetopotactic rearrangement of a germanium-rich CIT-13 germanosilicatehaving the same or similar Si/Ge. In other Aspects of this Embodiment,the composition may be described as comprising a double zig-zag chainsof germania joining and holding separate substantially parallelsilica-containing cfi-layers.

Embodiment 11

The crystalline silicate composition of Embodiment 9 or 10, wherein thegermanosilicate composition having CIT-5 topology is prepared byapplying heat, steam, or both heat and steam in the substantial absenceof mineral acid to the crystalline microporous CIT-13germanosilicatecomposition designated CIT-13 composition having a Si/Ge ratio in arange of from about 3.8 to about 5.

Embodiment 12

The crystalline silicate composition of Embodiment 1 or 2, whichcomprises a crystalline microporous germanosilicate composition havingCIT-5 topology and a Si/Ge ratio in a range of from about 5 to about250. In certain Aspects of this Embodiment, the Si/Ge ratio is in atleast one of the ranges of from about 5 to about 10, from about 10 toabout 20, from about 20 to about 30, from about 30 to about 40, fromabout 40 to about 50, from about 50 to about 100, from about 100 toabout 150, from about 150 to about 200, or from about 200 to about 250.In other Aspects of this Embodiment, the CIT-5 germanosilicatecomposition is derived from the reaction of mineral acid with agermania-rich CIT-5 germanosilicate having a Si/Ge ratio in a range offrom about 3.8 to about 5, or as described in any one of Embodiments 9to 11.

Embodiment 13

The crystalline silicate composition of Embodiment 12, furthercomprising at least one oxide of a metal or metalloid, M, where M isaluminum, boron, gallium, hafnium, iron, silicon, tin, titanium,vanadium, zinc, or zirconium, in a Si/M ratio in a range from about 25to about 250. In certain Aspects of this Embodiment, the Si/M ratio isin range from about 25 to about 50, from 50 to about 100, from about 100to about 125, from about 125 to about 150, from about 150 to about 200,from about 200 to about 250, from about 250 to about 500, from 500 toinfinity, or any combination of two or more of these ranges. In certainAspects of this Embodiment, the composition is one that has beenprepared by the reaction of a concentrated mineral acid and a source ofthe metal or metalloid oxide with a germania-rich CIT-5 germanosilicateof any one of Embodiments 9 to 11, under conditions described herein forthis conversion. In other Aspects of this Embodiment, the crystallinesilicate composition may be characterized as having silica-richcfi-layers connected by units comprising at least one oxide of aluminum,boron, gallium, hafnium, iron, silicon, tin, titanium, vanadium, zinc,or zirconium.

Embodiment 14

The crystalline silicate composition of Embodiment 1 or 2, designatedCIT-13P, that is a phyllosilicate comprising siloxylated silica-richcfi-layers having a Si/Ge ratio in a range of from about 30 to about250, or from about 50 to about 100. In certain Aspects of thisEmbodiment, the phyllosilicate, when stacked, exhibits a PXRD patterncharacterized by two major peaks in a range of from about 6 to about 92-θ. In other Aspects of this Embodiment, the phyllosilicate transformsto the germanosilicate CIT-15 on calcination. In still other Aspects ofthis Embodiment, the phyllosilicate transforms to the germanosilicateCIT-14 under pillaring conditions.

Embodiment 15

The crystalline silicate composition of Embodiment 14, wherein thephyllosilicate exhibits two major peak in the PXRD pattern is a peak ina range of from about 7.2 (±0.2) degrees 2-θ to about 8.2 (±0.2) degrees2-θ.

Embodiment 16

The crystalline silicate composition of Embodiment 14 or 15, whichexhibits a ²⁹Si and ¹H-²⁹Si CP MAS NMR spectrum having the chemicalshifts as shown in FIG. 26. In certain Aspects of this Embodiment, therelative intensities of Q4/Q3 peaks is in a range of from 2:1 to 1:1

Embodiment 17

The crystalline silicate composition of Embodiment 1 or 2, designatedCIT-14, that is a crystalline microporous germanosilicate having a Si/Geratio in a range of from about 25 to infinity. In some Aspects, theSi/Ge ratio is defined by at least on range of from about 25 to about50, from about 50 to about 75, from about 75 to about 100, from about100 to about 150, from about 150 to about 250, from about 250 to about500, or from about 500 to about infinity (i.e., germania-free). In someAspects, the CIT-14 germanosilicate exhibits a PXRD pattern having atleast five of the characteristic peaks of Table 9. In certain Aspects ofthis Embodiment, the PXRD pattern is substantially as shown in FIG. 32or FIG. 33. In other Aspects of this Embodiment, the CIT-14germanosilicate is derived from the pillaring synthesis describedelsewhere herein.

Embodiment 18

The crystalline silicate composition of any one of Embodiments 1, 2, or17, designated CIT-14, that comprises a three dimensional frameworkhaving pore channels defined by 8- and 12-membered rings. In certainAspects of this Embodiment, the pore channel dimensions of the 8- and12-membered rings are 4.0×3.4 Å and 6.9×5.4 Å, respectively.

Embodiment 19

The crystalline silicate composition of any one of Embodiments 1, 2, 17,or 18, designated CIT-14, which exhibits at least one of:

(a) a powder X-ray diffraction (XRD) pattern exhibiting at least five ofthe characteristic peaks at 7.55±0.2, 8.06±0.2, 12.79±0.2, 18.82±0.2,19.04±0.2, 20.67±0.2, 22.07±0.2, 24.36±0.2, 27.01±0.2, and 27.48±0.2degrees 2-θ; as shown in FIG. 34(A); or

(b) a powder X-ray diffraction (XRD) pattern substantially the same asshown in FIG. 32 or 33

Embodiment 20

The crystalline silicate composition of Embodiment 1 or 2 that is acrystalline microporous germanosilicate composition of CIT-15 topologycomprising a three dimensional framework and having pore channelsdefined by 10-membered rings. In some Aspects of this Embodiment, thepore dimensions of the 10-membered rings are 5.6 Å×3.8 Å. In someAspects of this Embodiment, the CIT-15 germanosilicate is derived fromthe calcination of the CIT-13P material, described herein.

Embodiment 21

The crystalline silicate composition of any one of Embodiments 1, 2, or20 which exhibits at least one of:

(a) a powder X-ray diffraction (XRD) pattern exhibiting at least five ofthe characteristic peaks at 8.15±0.2, 10.13±0.2, 12.80±0.2, 16.35±0.2,19.03±0.2, 19.97±0.2, 20.33±0.2, 23.79±0.2, 23.91±0.2, 24.10±0.2,24.63±0.2, 25.77±0.2, 26.41±0.2, 27.75±0.2, 34.73±0.2, and 37.78±0.2degrees 2-θ;

(b) a powder X-ray diffraction (XRD) pattern substantially the same asshown in FIG. 28 or 31; or

(c) unit cell parameters substantially equal to the following at:

Space group Cmmm a (Å) 17.4686(5) b (Å) 13.8271(2) c (Å) 5.1665(2) α = β= γ 90° Space Group 65 (Cmmm)

Embodiment 22

The crystalline silicate composition of Embodiment 21 which exhibits apowder X-ray diffraction (XRD) pattern exhibiting at least ten of thecharacteristic at 8.15±0.2, 10.13±0.2, 12.80±0.2, 16.35±0.2, 19.03±0.2,19.97±0.2, 20.33±0.2, 23.79±0.2, 23.91±0.2, 24.10±0.2, 24.63±0.2,25.77±0.2, 26.41±0.2, 27.75±0.2, 34.73±0.2, and 37.78±0.2 degrees 2-θ.

Embodiment 23

The crystalline silicate composition of any one of Embodiments 20 to 22,having a Si/Ge ratio in a range of from 25 to infinity. In some Aspects,the Si/Ge ratio is defined by at least on range of from about 25 toabout 50, from about 50 to about 75, from about 75 to about 100, fromabout 100 to about 150, from about 150 to about 250, from about 250 toabout 500, or from about 500 to about infinity (i.e., germania-free).

Embodiment 24

The crystalline silicate composition of any one of Embodiments 1 to 23,in its hydrogen form.

Embodiment 25

The crystalline microporous silicate or germanosilicate composition ofany one of Embodiments 1 to 13 or 17 to 23, further comprising a metalcation salt, a transition metal, a transition metal oxide, or atransition metal salt in its micropores. In specific Aspects of thisEmbodiments, the metal cation salt, a transition metal, a transitionmetal oxide, or a transition metal salt is any one elsewhere describedherein for this purpose

Embodiment 26

A catalyst comprising the crystalline microporous silicate compositionof any one of Embodiments 1 to 13 or 17 to 25.

Embodiment 27

A process for affecting an organic transformation, the processcomprising:

(a) carbonylating DME with CO at low temperatures;

(b) reducing NOx with methane:

(c) cracking, hydrocracking, or dehydrogenating a hydrocarbon;

(d) dewaxing a hydrocarbon feedstock;

(d) converting paraffins to aromatics:

(e) isomerizing or disproportionating an aromatic feedstock;

(f) alkylating an aromatic hydrocarbon;

(g) oligomerizing an alkene;

(h) aminating a lower alcohol;

(i) separating and sorbing a lower alkane from a hydrocarbon feedstock;

(j) isomerizing an olefin;

(k) producing a higher molecular weight hydrocarbon from lower molecularweight hydrocarbon;

(l) reforming a hydrocarbon

(m) converting a lower alcohol or other oxygenated hydrocarbon toproduce an olefin product (including MTO);

(n) epoxiding olefins with hydrogen peroxide;

(o) reducing the content of an oxide of nitrogen contained in a gasstream in the presence of oxygen;

(p) separating nitrogen from a nitrogen-containing gas mixture; or

(q) converting synthesis gas containing hydrogen and carbon monoxide toa hydrocarbon stream; or

(r) reducing the concentration of an organic halide in an initialhydrocarbon product;

by contacting the respective feedstock with the catalyst of Embodiment26, under conditions sufficient to affect the named transformation.

Embodiment 28

A method comprising calcining a crystalline microporous CIT-13germanosilicate composition, having a Si/Ge ratio in a range of fromabout 3.8 to about 5.4, at a temperature in a range of from about 450°C. to about 1200° C., optionally in the presence of steam, but in theabsence of mineral acid, for a time sufficient so as to convert theCIT-13 germanosilicate to a germanosilicate composition of CIT-5topology. In certain Aspects of this Embodiment, the Si/Ge ratio of theCIT-5 germanosilicate is the same as or similar to that of the CIT-13germanosilicate. In certain Aspects of this Embodiment, the synthesis ofthe precursor CIT is done in a static oven. In other Aspects, thesynthesis is done in a moving chamber, preferably a rotating oven. Inother Aspects of this Embodiment, the calcining is done in the presenceof steam. In other Aspects, the calcining is done before or after theapplication of steam preferably at a temperature in a range of from 600°C. to about 1000° C., preferably in a range of from 700° C. to 900° C.In other Aspects, the CIT-5 germanosilicate is isolated.

Embodiment 29

The method of Embodiment 28, further comprising subjecting the CIT-5germanosilicate to concentrated mineral acid under conditions sufficient(e.g., 175° C.-190° C. for 24 hours) to degermanate at least a portionof the CIT-5 germanosilicate, so as to produce a CIT-5 germanosilicatewith a Si/Ge ratio in a range of from about 25 to about 250. In otherAspects, the product CIT-5 germanosilicate is isolated.

Embodiment 30

The method of Embodiment 28, further comprising subjecting the CIT-5germanosilicate to concentrated mineral acid in the presence of a sourceof a metal or metalloid oxide, M, where M is aluminum, boron, gallium,hafnium, iron, silicon, tin, titanium, vanadium, zinc, or zirconium,preferably aluminum, under conditions sufficient (e.g., 175° C.-190° C.for 24 hours) to degermanate at least a portion of the CIT-5germanosilicate, so as to produce a CIT-5 germanosilicate with a Si/Geratio in a range of from about 25 to about 250 and with a Si/M ratio ina range from about 25 to about 250. In other Aspects, the product CIT-5germanosilicate is isolated.

Embodiment 31

A method comprising treating a crystalline microporous CIT-13germanosilicate composition, having a Si/Ge ratio in a range of fromabout 4.5 to about 10, with a concentrated mineral acid (e.g., ca. 1 M)under conditions sufficient (e.g., 175° C.−190° C. for 24 hours) todegermanate at least a portion of the CIT-13 germanosilicate, so as toproduce a CIT-13 germanosilicate with a Si/Ge ratio in a range of fromabout 25 to about 250. In other Aspects, the product CIT-13germanosilicate is isolated.

Embodiment 32

The method of Embodiment 31, further comprising subjecting the CIT-13germanosilicate to concentrated mineral acid in the presence of a sourceof a metal or metalloid oxide, M, where M is aluminum, boron, gallium,hafnium, iron, silicon, tin, titanium, vanadium, zinc, or zirconium,preferably aluminum, under conditions sufficient (e.g., 175° C.-190° C.for 24 hours) to degermanate at least a portion of the CIT-13germanosilicate, so as to produce a CIT-13 germanosilicate with a Si/Geratio in a range of from about 25 to about 250 and with a Si/M ratio ina range from about 25 to about 250. In other Aspects, the product CIT-13germanosilicate is isolated.

Embodiment 33

A method comprising treating a crystalline microporous CIT-13germanosilicate composition, having a Si/Ge ratio in a range of fromabout 3.8 to about 5.4, with a dilute mineral acid (e.g., ca. 0.1 M)under conditions sufficient (e.g., 90° C.−110° C. for 24 hours) todelaminate at least a portion of the CIT-13 germanosilicate to formCIT-13P, as described elsewhere herein. In other Aspects, the productCIT-13P germanosilicate is isolated.

Embodiment 34

The method of Embodiment 34, further comprising calcining the CIT-13Punder conditions sufficient (e.g., 580° C.−750° C. for 6 to 8 hours, inthe presence of absence of C1-12 alkyl amines) to form a germanosilicateof CIT-15 topology.

Embodiment 35

The method of Embodiment 34, further comprising subjecting the CIT-13Pto conditions consistent with a pillaring reaction, for example treatingwith a concentrated (e.g., ca. 1 M) mineral acid in the presence of asilica source under conditions to form a alkoxylated intermediate (e.g.,175° C. for 18-24 hours) followed by calcining the alkoxylatedintermediate under conditions sufficient (e.g., 580° C. to 750° C. for6-8 hours) to form a CIT-14 germanosilicate.

EXAMPLES

The following Examples provide the experimental methods used tocharacterize these novel materials as well as illustrate some of theconcepts described within this disclosure. While each Example, bothprovided here and elsewhere in the body of the specification, isconsidered to provide specific individual embodiments of composition,methods of preparation and use, none of the Examples should beconsidered to limit the more general embodiments described herein.

In the following examples, efforts have been made to ensure accuracywith respect to numbers used (e.g. amounts, temperature, etc.) but someexperimental error and deviation should be accounted for. Unlessindicated otherwise, temperature is in degrees C., pressure is at ornear atmospheric.

Example 1: Materials and Methods

Unless otherwise noted, all reagents were purchased from commercialsources and were used as received. Unless otherwise noted all, reactionswere conducted in flame-dried glassware under an atmosphere of argon.Hydroxide ion exchanges were performed using OH-formstyrene-divinylbenzene (DVB)-matrix ion exchange resin (DOWEX™ MARATHON™A) with an exchange capacity of 1 meq/mL. Titrations were performedusing a Mettler-Toledo DL22 autotitrator using 0.01 M HCl as thetitrant. All liquid NMR spectra were recorded with a 500 MHz VarianSpectrometer. Liquid NMR spectra were recorded on Varian Mercuryspectrometers.

All powder x-ray diffraction characterization were conducted on a RigakuMiniFlex II diffractometer with Cu Kα radiation.

Solid-state ²⁹Si MAS NMR and ²⁷Al MAS NMR spectra were obtained using aBruker DSX-500 spectrometer (11.7 T) and a Bruker 4 mm MAS probe. Thespectral operating frequency was 99.4 MHz for the ²⁹Si nuclei and 78.2MHz for the ²⁷Al nuclei using a 90° pulse length of 2 μs and a cycledelay time of 1 s. Spectra were referenced to external tetramethylsilane(TMS) standard for ²⁹Si and a 1 M aqueous aluminum nitrate solution for²⁷Al. Samples were spun at 8 kHz for ²⁹Si MAS and CPMAS NMR experimentsand 12 kHz for ²⁷Al MAS.

An Oxford X-Max SDD X-ray Energy Dispersive Spectrometer (EDS) systemwas used for determining the Si/Al and Si/Ge ratios of the samples. Allpowder x-ray diffraction (PXRD) characterization was conducted on aRigaku MiniFlex II with Cu Kα radiation. Elemental analysis of calcinedzeolite samples was performed using EDS.

SEM analyses were performed on a ZEISS 1550 VP FESEM, equipped with anOxford X-Max SDD X-ray Energy Dispersive Spectrometer (EDS) system fordetermining the elemental ratios of the samples.

Example 2. Preparation of CIT-13P

100 mg of freshly calcined CIT-13 was dispersed in 160 ml of 0.1 N HClaqueous solution. The mixture was stirred at 99° C. for 24 hours. Afterthat, the solid was filtrated and dried at room temperature. The yieldof this delamination is typically about 60-70%. The XRD peakcorresponding to the interlayer diffraction of CIT-13P is about8.19-8.20°. (complete removal of d4r) Otherwise (2theta<8°)

As those skilled in the art will appreciate, numerous modifications andvariations of the present invention are possible in light of theseteachings, and all such are contemplated hereby. All references citedherein are incorporated by reference herein, at least for theirteachings in the context presented.

What is claimed:
 1. A crystalline microporous silicate compositioncomprising a three-dimensional framework having pore channels defined by10-membered rings, the crystalline microporous silicate compositionhaving a Si/Ge ratio of from 25 to infinity and having a an x-raydiffraction (XRD) pattern with characteristic peaks at 8.15±0.2,10.13±0.2, 12.80±0.2, 16.35±0.2, 20.33±0.2, and 25.77±0.2 degrees 2-θ,wherein the peak at 10.13±0.2 degrees 2-θ is the most intense peak inthe X-ray diffraction (XRD) pattern.
 2. The crystalline microporoussilicate composition of claim 1, further comprising at least one oxideof a metal or metalloid, M, where M is aluminum, boron, gallium,hafnium, iron, tin, titanium, vanadium, zinc, or zirconium.
 3. Thecrystalline microporous silicate composition of claim 1 that exhibits atleast one of: (a) a powder X-ray diffraction (XRD) pattern having atleast eight of the characteristic peaks at 8.15±0.2, 10.13±0.2,12.80±0.2, 16.35±0.2, 19.03±0.2, 19.97±0.2, 20.33±0.2, 23.79±0.2,23.91±0.2, 24.10±0.2, 24.63±0.2, 25.77±0.2, 26.41±0.2, 27.75±0.2,34.73±0.2, and 37.78±0.2, degrees 2-θ, including those set forth inclaim 1, wherein the park at 10.13±0.2 degrees 2-θ is the most intensepeak in the X-ray diffraction (XRD) pattern; (b) a powder X-raydiffraction (XRD) pattern substantially the same as shown in FIG. 27 or29; or (c) unit cell parameters substantially equal to the following:Space group Cmmm a (Å) 17.4686(5) b (Å) 13.8271(2) c (Å) 5.1665(2) α = β= γ 90° Space Group 65 (Cmmm).


4. The crystalline microporous silicate composition of claim 1 thatexhibits a powder X-ray diffraction (XRD) pattern having characteristicpeaks at 8.15±0.2, 10.13±0.2, 12.80±0.2, 16.35±0.2, 19.03±0.2,19.97±0.2, 20.33±0.2, 23.79±0.2, 23.91±0.2, 24.10±0.2, 24.63±0.2,25.77±0.2, 26.41±0.2, 34.73±0.2, and 37.78±0.2 degrees 2-θ, includingthose peaks set forth in claim 1, wherein the peak at 10.13±0.2 degrees2-θ is the most intense peak in the X-ray diffraction (XRD) pattern. 5.The crystalline microporous silicate composition of claim 4 thatexhibits a powder X-ray diffraction (XRD) pattern having at least ten ofthe characteristic peaks at 8.15±0.2, 10.13±0.2, 12.80±0.2, 16.35±0.2,19.03±0.2, 19.97±0.2, 20.33±0.2, 23.79±0.2, 23.91±0.2, 24.10±0.2,24.63±0.2, 25.77±0.2, 26.41±0.2, 27.75±0.2, 34.73±0.2, and 37.78±0.2degrees 2-θ, including those peaks set forth in claim 1, wherein thepeak at 10.13±0.2 degrees 2-θ is the most intense peak in the X-raydiffraction (XRD) pattern.
 6. The crystalline microporous silicatecomposition of claim 1 that exhibits a powder X-ray diffraction (XRD)pattern substantially the same as shown in FIG. 27 or
 29. 7. Thecrystalline microporous silicate composition of claim 1 having unit cellparameters substantially equal to the following: Space group Cmmm a (Å)17.4686(5) b (Å) 13.8271(2) c (Å)  5.1665(2) a = β = γ 90° Space Group65 (Cmmm).


8. The crystalline microporous silicate composition of claim 1, whereinthe pore channels defined by 10-membered rings have channel dimensionsof 5.6 Å×3.8 Å.
 9. The crystalline microporous silicate composition ofclaim 1, in its hydrogen form.
 10. The crystalline microporous silicatecomposition of claim 1, further comprising a metal cation salt, atransition metal, a transition metal oxide, or a transition metal saltin its micropores.
 11. The crystalline microporous silicate compositionof claim 1 that is a germanosilicate having a Si/Ge ratio of from 25 to200.
 12. The crystalline microporous germanosilicate composition ofclaim 11 having a Si/Ge ratio of from 50 to
 100. 13. The crystallinemicroporous germanosilicate composition of claim 11 that exhibits atleast one of: (a) a powder X-ray diffraction (XRD) pattern having atleast eight of the characteristic peaks at 8.15±0.2, 10.13±0.2,12.80±0.2, 16.35±0.2, 19.03±0.2, 19.97±0.2, 20.33±0.2, 23.79±0.2,23.91±0.2, 24.10±0.2, 24.63±0.2, 25.77±0.2, 26.41±0.2, 27.75±0.2,34.73±0.2, and 37.78±0.2 degrees 2-θ, wherein the peak at 10.13±0.2degrees 2-θ is the most intense peak in the X-ray diffraction (XRD)pattern; (b) a powder X-ray diffraction (XRD) pattern substantially thesame as shown in FIG. 27 or 29; or (c) unit cell parameterssubstantially equal to the following: Space group Cmmm a (Å) 17.4686(5)b (Å) 13.8271(2) c (Å)  5.1665(2) a = β = γ 900 Space Group 65 (Cmmm).


14. The crystalline microporous germanosilicate composition of claim 11that exhibits a powder X-ray diffraction (XRD) pattern havingcharacteristic peaks at 8.15±0.2, 10.13±0.2, 12.80±0.2, 16.35±0.2,19.03±0.2, 19.97±0.2, 20.33±0.2, 23.79±0.2, 23.91±0.2, 24.10±0.2,24.63±0.2, 25.77±0.2, 26.41±0.2, 27.75±0.2, 34.73±0.2, and 37.78±0.2degrees 2-θ, wherein the peak at 10.13±0.2 degrees 2-θ is the mostintense peak in the X-ray diffraction (XRD) pattern.
 15. The crystallinemicroporous germanosilicate composition of claim 14 that exhibits apowder X-ray diffraction (XRD) pattern having at least ten of thecharacteristic peaks at 8.15±0.2, 10.13±0.2, 12.80±0.2, 16.35±0.2,19.03±0.2, 19.97±0.2, 20.33±0.2, 23.79±0.2, 23.91±0.2, 24.10±0.2,24.63±0.2, 25.77±0.2, 26.41±0.2, 27.75±0.2, 34.73±0.2, and 37.78±0.2degrees 2-θ, wherein the peak at 10.13±0.2 degrees 2-θ is the mostintense peak in the X-ray diffraction (XRD) pattern.
 16. The crystallinemicroporous silicate composition of claim 11 that exhibits a powderX-ray diffraction (XRD) pattern substantially the same as shown in FIG.27 or
 29. 17. The crystalline microporous silicate composition of claim11 having unit cell parameters substantially equal to the following:Space group Cmmm a (Å) 17.4686(5) b (Å) 13.8271(2) c (Å)  5.1665(2) a =β = γ 900 Space Group 65 (Cmmm).


18. The crystalline microporous germanosilicate composition of claim 11,wherein the pore channels defined by 10-membered rings have channeldimensions of 5.6 Å×3.8 Å.
 19. The crystalline microporous silicatecomposition of claim 11, in its hydrogen form.
 20. The crystallinemicroporous germanosilicate composition of claim 11, further comprisinga metal cation salt, a transition metal, a transition metal oxide, or atransition metal salt in its micropores.
 21. A method of preparing thecrystalline microporous germanosilicate composition of claim 11, themethod comprising calcining a phyllosilicate of CIT-13P topology underconditions sufficient to form the crystalline microporousgermanosilicate composition of CIT-15 topology.
 22. The method of claim21 comprising calcining a phyllosilicate of CIT-13P topology at atemperature in a range of from 400° C. to 950° C., thereby producing thecrystalline germanosilicate composition designated CIT-15, the calciningoptionally done in the presence of a C₁₋₁₂ alkyl amine, thephyllosilicate comprising siloxylated silica-rich cfi-layers having aSi/Ge ratio in a range of from 25 to 250, wherein the phyllosilicatedesignated CIT-13P is characterized as exhibiting one or both of: (i)two major peaks in the PXRD pattern a range of from 7.2 (±0.2) degrees2-θ to 8.2 (±0.2) degrees 2-θ; or (ii) a ²⁹Si MAS NMR spectrum showingcharacteristic peaks at chemical shifts of −105 ppm and −113 ppm or an¹H-²⁹Si CP MAS NMR spectrum showing peaks at −94 ppm, −105 ppm, and −113ppm, relative to tetramethylsilane (TMS).
 23. A catalyst comprising thecrystalline microporous germanosilicate composition claim 11, thecatalyst further optionally comprising at least one metal cation salt,transition metal, transition metal oxide, or transition metal salt inits micropores.
 24. A process for affecting an organic transformation,the process comprising: (a) carbonylating DME with CO at lowtemperatures; (b) reducing NOx with methane; (c) cracking,hydrocracking, or dehydrogenating a hydrocarbon; (d) dewaxing ahydrocarbon feedstock; (e) converting paraffins to aromatic; (f)isomerizing or disproportionating an aromatic feedstock; (g) alkylatingan aromatic hydrocarbon; (h) oligomerizing an alkene; (i) aminating alower alcohol; (j) separating and sorbing a lower alkane from ahydrocarbon feedstock; (k) isomerizing an olefin; (l) producing a highermolecular weight hydrocarbon from lower molecular weight hydrocarbon;(m) reforming a hydrocarbon; (n) converting a lower alcohol or otheroxygenated hydrocarbon to produce an olefin product (including MTO); (o)epoxidizing olefins with hydrogen peroxide; (p) reducing the content ofan oxide of nitrogen contained in a gas stream in the presence ofoxygen; (q) separating nitrogen from a nitrogen-containing gas mixture;or (r) converting synthesis gas containing hydrogen and carbon monoxideto a hydrocarbon stream; or (s) reducing the concentration of an organichalide in an initial hydrocarbon product; by contacting the respectivefeedstock with the catalyst of claim 23, under conditions sufficient toaffect the named transformation.
 25. A catalyst comprising thecrystalline microporous germanosilicate composition claim 1, thecatalyst further optionally comprising at least one metal cation salt,transition metal, transition metal oxide, or transition metal salt inits micropores.
 26. A process for affecting an organic transformation,the process comprising: (a) carbonylating DME with CO at lowtemperatures; (b) reducing NOx with methane: (c) cracking,hydrocracking, or dehydrogenating a hydrocarbon; (d) dewaxing ahydrocarbon feedstock; (e) converting paraffins to aromatics: (f)isomerizing or disproportionating an aromatic feedstock; (g) alkylatingan aromatic hydrocarbon; (h) oligomerizing an alkene; (i) aminating alower alcohol; (j) separating and sorbing a lower alkane from ahydrocarbon feedstock; (k) isomerizing an olefin; (l) producing a highermolecular weight hydrocarbon from lower molecular weight hydrocarbon;(m) reforming a hydrocarbon (n) converting a lower alcohol or otheroxygenated hydrocarbon to produce an olefin product (including MTO); (o)epoxidizing olefins with hydrogen peroxide; (p) reducing the content ofan oxide of nitrogen contained in a gas stream in the presence ofoxygen; (q) separating nitrogen from a nitrogen-containing gas mixture;or (r) converting synthesis gas containing hydrogen and carbon monoxideto a hydrocarbon stream; or (s) reducing the concentration of an organichalide in an initial hydrocarbon product; by contacting the respectivefeedstock with the catalyst of claim 25, under conditions sufficient toaffect the named transformation.